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Corrosion Science
and Technology
Third Edition
Corrosion Science
and Technology
Third Edition

David E.J. Talbot

James D.R. Talbot
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742

© 2018 by Taylor & Francis Group, LLC

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Contents

Preface to the Third Edition...................................................................................................... xxv

Authors....................................................................................................................................... xxvii

1 Overview of Corrosion and Protection Strategies............................................................ 1

1.1 Corrosion in Aqueous Media....................................................................................... 1
1.1.1 Corrosion as a System Characteristic.............................................................1
1.1.2 The Electrochemical Origin of Corrosion..................................................... 2
1.1.3 Stimulated Local Corrosion.............................................................................2
1.2 Thermal Oxidation......................................................................................................... 3
1.2.1 Protective Oxides.............................................................................................. 3
1.2.2 Nonprotective Oxides......................................................................................4
1.3 Environmentally Sensitive Cracking.......................................................................... 4
1.4 Strategies for Corrosion Control.................................................................................. 4
1.4.1 Passivity............................................................................................................. 4
1.4.2 Conditions in the Environment...................................................................... 5
1.4.3 Cathodic Protection..........................................................................................5
1.4.4 Protective Coatings...........................................................................................5
1.4.5 Corrosion Costs................................................................................................. 6
1.4.6 Criteria for Corrosion Failure..........................................................................6
1.4.7 Material Selection.............................................................................................7
1.4.8 Geometric Factors............................................................................................. 7
1.5 Some Symbols, Conventions and Equations.............................................................. 8
1.5.1 Ions and Ionic Equations.................................................................................8
1.5.2 Partial Reactions...............................................................................................9
1.5.3 Representation of Corrosion Processes....................................................... 10
1.5.3.1 Active Dissolution of Iron with Oxygen Absorption................. 10
1.5.3.2 Passivity of Iron in Alkaline Water.............................................. 11
Further Reading...................................................................................................................... 11

2 Structures Participating in Corrosion Processes............................................................ 13

2.1 Origins and Characteristics of Structure.................................................................. 13
2.1.1 Phases............................................................................................................... 13
2.1.1.1 Crystalline Solids............................................................................ 13
2.1.1.2 Liquids.............................................................................................. 17
2.1.1.3 Non-Crystalline Solids................................................................... 18
2.1.1.4 Gases................................................................................................. 18
2.1.2 The Role of Electrons in Bonding................................................................. 18
2.1.2.1 Atomic Orbitals............................................................................... 19
2.1.2.2 Molecular Orbitals and Bonding of Atoms................................. 21
2.1.3 The Concept of Activity.................................................................................22
2.2 The Structure of Water and Aqueous Solutions...................................................... 23
2.2.1 The Nature of Water....................................................................................... 23
2.2.2 The Water Molecule........................................................................................ 24
2.2.3 Liquid Water.................................................................................................... 25

v
vi Contents

2.2.3.1 Hydrogen Bonding......................................................................... 25

2.2.3.2 Dielectric Constant.......................................................................... 25
2.2.3.3 Viscosity............................................................................................ 26
2.2.4 Autodissociation and pH of Aqueous Solutions........................................ 26
2.2.5 The pH Scale.................................................................................................... 27
2.2.6 Foreign Ions in Solution................................................................................. 28
2.2.7 Ion Mobility..................................................................................................... 29
2.2.8 Structures of Water and Ionic Solutions at Metal Surfaces....................... 31
2.2.9 Constitutions of Hard and Soft Natural Waters......................................... 32
2.2.9.1 Rainwater......................................................................................... 32
2.2.9.2 Hard Waters..................................................................................... 35
2.3 The Structures of Metal Oxides................................................................................. 36
2.3.1 Electronegativity............................................................................................. 37
2.3.2 Partial Ionic Character of Metal Oxides...................................................... 38
2.3.3 Oxide Crystal Structures............................................................................... 39
2.3.3.1 Simple Cubic Structures (Rock Salt, NaCl Structure)................ 40
2.3.3.2 Rhombohedral–Hexagonal Structures (Corundum Structure).... 40
2.3.3.3 Rutile Structures.............................................................................. 41
2.3.3.4 Spinel Structures............................................................................. 41
2.3.3.5 Brucite Structures............................................................................ 41
2.3.3.6 Other Structures.............................................................................. 41
2.3.4 Conduction and Valence Electron Energy Bands......................................42
2.3.5 The Origins of Lattice Defects in Metal Oxides.........................................42
2.3.5.1 General Approach...........................................................................43
2.3.5.2 Configurational Entropy of Atoms or Ions on a Lattice............44
2.3.5.3 Equilibrium Number of Defects...................................................44
2.3.5.4 Nature of Defects in Oxide Lattices............................................. 46
2.3.5.5 Representation of Defects.............................................................. 46
2.3.6 Classification of Oxides by Defect Type...................................................... 47
2.3.6.1 Stoichiometric Oxides..................................................................... 47
2.3.6.2 Cation Excess Oxides...................................................................... 47
2.3.6.3 Cation Deficit Oxides...................................................................... 48
2.3.6.4 Anion Deficit Oxides...................................................................... 49
2.3.6.5 Intrinsic Semiconductors............................................................... 49
2.3.6.6 Degrees of Non-Stoichiometry...................................................... 49
2.4 The Structures of Metals............................................................................................. 50
2.4.1 The Metallic Bond........................................................................................... 50
2.4.2 Crystal Structures and Lattice Defects........................................................ 51
2.4.3 Phase Equilibria.............................................................................................. 51
2.4.3.1 Solid Solutions.................................................................................54
2.4.3.2 Eutectic Transformations...............................................................54
2.4.3.3 Peritectic Transformations............................................................. 55
2.4.3.4 Eutectoid Transformations............................................................. 55
2.4.3.5 Intermetallic Compound Formation............................................ 55
2.4.3.6 Real Systems..................................................................................... 55
2.4.4 Structural Artefacts Introduced during Manufacture.............................. 56
2.4.4.1 Structural Features of Castings and Ingots................................. 56
2.4.4.2 Characteristics Imparted by Mechanical Working.................... 57
Further Reading...................................................................................................................... 57
Contents vii

3 Thermodynamics and Kinetics of Corrosion Processes................................................ 59

3.1 Thermodynamics of Aqueous Corrosion................................................................. 59
3.1.1 Oxidation and Reduction Processes in Aqueous Solution....................... 59
3.1.1.1 Oxidation States............................................................................... 59
3.1.1.2 Electrodes......................................................................................... 61
3.1.2 Equilibria at Electrodes and the Nernst Equation..................................... 62
3.1.3 Standard State for Activities of Ions in Solution........................................63
3.1.4 Electrode Potentials........................................................................................63
3.1.4.1 Convention for Representing Electrodes at Equilibrium..........63
3.1.4.2 Choice of a Potential Scale.............................................................64
3.1.4.3 The Standard Hydrogen Electrode...............................................64
3.1.5 Pourbaix (Potential-pH) Diagrams............................................................... 67
3.1.5.1 Principle and Purpose.................................................................... 67
3.1.5.2 Example of the Construction of a Diagram – The
Iron–Water System.......................................................................... 67
3.1.5.3 The Domain of Stability for Water................................................ 72
3.1.5.4 Application of Pourbaix Diagrams to Corrosion Problems...... 72
3.1.5.5 Pourbaix Diagrams for Some Metals of Interest in Corrosion......73
3.1.5.6 Limitations of Pourbaix Diagrams...............................................80
3.2 Kinetics of Aqueous Corrosion..................................................................................80
3.2.1 Kinetic View of Equilibrium at an Electrode.............................................. 81
3.2.2 Polarization...................................................................................................... 82
3.2.2.1 Activation Polarization...................................................................83
3.2.2.2 Concentration Polarization............................................................85
3.2.2.3 Resistance Polarization................................................................... 86
3.2.2.4 The Hydrogen Evolution Reaction and Hydrogen
Overpotential................................................................................... 87
3.2.2.5 The Oxygen Reduction Reaction................................................... 89
3.2.3 Polarization Characteristics and Corrosion Velocities.............................. 89
3.2.3.1 Corrosion Velocity Diagrams........................................................ 89
3.2.3.2 Differential Polarization for Oxygen Reduction and
Crevice Corrosion............................................................................ 93
3.2.4 Passivity........................................................................................................... 93
3.2.4.1 Spontaneous Passivation................................................................ 93
3.2.4.2 Anodic Passivation.......................................................................... 94
3.2.4.3 Theories of Passivation................................................................... 94
3.2.5 Breakdown of Passivity.................................................................................. 96
3.2.5.1 General Breakdown of Passivity................................................... 96
3.2.5.2 Local Breakdown of Passivity....................................................... 96
3.2.5.3 Mechanical Breakdown of Passivity............................................ 97
3.2.6 Corrosion Inhibitors....................................................................................... 97
3.2.6.1 Cathodic Inhibitors......................................................................... 98
3.2.6.2 Anodic Inhibitors............................................................................ 98
3.3 Thermodynamics and Kinetics of Dry Oxidation................................................ 100
3.3.1 Factors Promoting the Formation of Protective Oxides.......................... 100
3.3.2 Thin Films and the Cabrera–Mott Theory................................................ 101
3.3.3 Thick Films, Thermal Activation and the Wagner Theory..................... 102
3.3.3.1 Oxidation of Metals Forming Cation Interstitial (n-type)
Oxides............................................................................................. 102
viii Contents

3.3.3.2 Oxidation of Metals Forming Cation Vacancy (p-type)

Oxides............................................................................................. 103
3.3.3.3 Oxidation of Metals Forming Anion Vacancy (n-type)
Oxides............................................................................................. 104
3.3.3.4 Oxidation of Metals Forming Stoichiometric Ionic Oxides.........105
3.3.3.5 Time and Temperature Dependence of
Diffusion-Controlled Oxidation................................................. 106
3.3.3.6 Correlations with Other Observations....................................... 106
3.3.3.7 Effects of Impurities...................................................................... 107
3.3.3.8 Loss of Integrity of Protective Oxides........................................ 108
3.3.4 Selective Oxidation of Components in an Alloy...................................... 108
3.3.4.1 Principles........................................................................................ 108
3.3.4.2 Oxidation of Alloys Forming Complex Oxides........................ 110
3.3.4.3 Kinetic Considerations................................................................. 114
Problems................................................................................................................................. 114
Appendix: Construction of Some Pourbaix Diagrams.................................................... 120
Further Reading.................................................................................................................... 137

4 Mixed Metal Systems......................................................................................................... 139

4.1 Galvanic Stimulation................................................................................................. 139
4.1.1 Bimetallic Couples........................................................................................ 139
4.1.2 The Origin of the Bimetallic Effect............................................................. 140
4.1.3 Design Implications...................................................................................... 141
4.1.3.1 Active and Weakly Passive Metals............................................. 141
4.1.3.2 Active/Passive Couples................................................................ 142
4.1.3.3 Cathodic Collectors....................................................................... 142
4.1.3.4 Compatibility Groups................................................................... 142
4.1.3.5 Indirect Stimulation...................................................................... 143
4.1.3.6 Variable Polarity............................................................................ 145
4.2 Galvanic Protection................................................................................................... 146
4.2.1 Principle......................................................................................................... 146
4.2.2 Galvanic Protection by Coatings................................................................ 146
4.2.2.1 Zinc Coatings on Steel.................................................................. 146

5 The Intervention of Stress................................................................................................. 147

5.1 Stress-Corrosion Cracking........................................................................................ 147
5.1.1 Characteristic Features................................................................................. 147
5.1.2 SCC in Aluminium Alloys.......................................................................... 149
5.1.2.1 Susceptible Alloys......................................................................... 149
5.1.2.2 Probable Causes............................................................................. 149
5.1.2.3 Mechanisms................................................................................... 149
5.1.3 SCC in Stainless Steels................................................................................. 151
5.1.3.1 Brief Description of the Phenomena........................................... 151
5.1.3.2 Environmental Influences............................................................ 151
5.1.3.3 Sensitivity to Steel Structure and Composition........................ 152
5.1.3.4 Mechanisms................................................................................... 152
5.1.4 Stress Corrosion Cracking in Plain Carbon Steels................................... 153
5.1.4.1 Brief General Description of the Phenomena............................ 153
5.1.4.2 Mechanisms................................................................................... 153
Contents ix

5.2 Corrosion Fatigue....................................................................................................... 154

5.2.1 Characteristic Features................................................................................. 154
5.2.2 Mechanisms................................................................................................... 155
5.2.2.1 Mechanical Events Causing Failure........................................... 155
5.2.2.2 Intervention of the Environment................................................ 155
5.3 Enhanced Corrosion in Flowing or Turbulent Aqueous Media......................... 156
5.3.1 Erosion–Corrosion........................................................................................ 156
5.3.2 Cavitation....................................................................................................... 156
5.4 Precautions against Stress-Induced Failures......................................................... 156
5.4.1 Materials......................................................................................................... 156
5.4.2 Environments................................................................................................ 157
5.4.3 Stresses........................................................................................................... 157
5.4.4 Geometry....................................................................................................... 157
5.4.5 Monitoring..................................................................................................... 157
Further Reading.................................................................................................................... 158

6 Protective Coatings............................................................................................................. 159

6.1 Surface Preparation.................................................................................................... 159
6.1.1 Surface Conditions of Manufactured Metal Forms................................. 159
6.1.1.1 Rolled Surfaces.............................................................................. 159
6.1.1.2 Extruded Surfaces......................................................................... 160
6.1.1.3 Surfaces of Press-Formed Products............................................ 160
6.1.2 The Cleaning and Preparation of Metal Surfaces.................................... 161
6.1.2.1 Descaling Steels............................................................................. 161
6.1.2.2 Cleaning Aluminium Surfaces................................................... 162
6.1.2.3 Preparation of Aluminium Substrates for Electrodeposits..... 163
6.1.2.4 Chemical and Electrochemical Polishing of Aluminium
Alloys.............................................................................................. 164
6.2 Electrodeposition....................................................................................................... 165
6.2.1 Application and Principles.......................................................................... 165
6.2.1.1 Cathodic and Anodic Reactions.................................................. 166
6.2.1.2 Hydrogen Discharge..................................................................... 166
6.2.1.3 Throwing Power............................................................................ 167
6.2.1.4 Illustrative Selection of Deposition Processes.......................... 168
6.2.2 Electrodeposition of Nickel......................................................................... 169
6.2.2.1 General Considerations................................................................ 169
6.2.2.2 Bright Nickel Plating..................................................................... 170
6.2.2.3 Other Nickel Plating Processes................................................... 171
6.2.2.4 Electroless Nickel/Phosphorus Plating..................................... 171
6.2.3 Electrodeposition of Copper....................................................................... 172
6.2.3.1 Acid Sulfate Baths......................................................................... 172
6.2.3.2 Alkaline Cyanide Baths................................................................ 172
6.2.4 Electrodeposition of Chromium................................................................. 173
6.2.4.1 Applications................................................................................... 173
6.2.4.2 Principles of Deposition............................................................... 173
6.2.4.3 Operation of Chromic Acid Baths.............................................. 174
6.2.4.4 Quality of the Deposit.................................................................. 174
6.2.5 Electrodeposition of Tin............................................................................... 175
6.2.5.1 General Principles......................................................................... 175
x Contents

6.2.5.2 Acid Tin Baths................................................................................ 176

6.2.5.3 Alkaline Stannate Baths............................................................... 177
6.2.5.4 Halide Baths................................................................................... 177
6.2.6 Electrodeposition of Zinc............................................................................. 178
6.2.6.1 Acid Sulfate Baths......................................................................... 178
6.2.6.2 Alkaline Cyanide Baths................................................................ 178
6.3 Hot-Dip Coatings....................................................................................................... 178
6.3.1 Zinc Coatings (Galvanizing)....................................................................... 179
6.3.2 Tin Coatings................................................................................................... 179
6.3.3 Aluminium Coatings................................................................................... 180
6.4 Conversion Coatings.................................................................................................. 180
6.4.1 Phosphating................................................................................................... 180
6.4.1.1 Mechanism of Phosphating......................................................... 180
6.4.1.2 Accelerated Phosphating Processes............................................ 181
6.4.2 Anodizing...................................................................................................... 182
6.4.2.1 Mechanism of Anodizing............................................................ 183
6.4.2.2 Practice............................................................................................ 183
6.4.2.3 Applications................................................................................... 184
6.4.3 Chromating.................................................................................................... 185
6.4.3.1 Coatings on Aluminium.............................................................. 186
6.4.3.2 Coatings on Zinc........................................................................... 187
6.4.3.3 Coatings on Magnesium Alloys.................................................. 188
6.5 Paint Coatings for Metals.......................................................................................... 188
6.5.1 Paint Components......................................................................................... 188
6.5.1.1 Binding Media............................................................................... 189
6.5.1.2 Pigments and Extenders............................................................... 191
6.5.1.3 Solvents........................................................................................... 191
6.5.2 Applications................................................................................................... 192
6.5.2.1 Traditional Paints.......................................................................... 192
6.5.2.2 Waterborne Paints......................................................................... 192
6.5.3 Paint Formulations....................................................................................... 193
6.5.4 Protection of Metals by Paint Systems....................................................... 193
Further Reading.................................................................................................................... 194

7 Corrosion of Iron and Steels............................................................................................. 195

7.1 Iron and Steel Microstructures................................................................................ 195
7.1.1 Solid Solutions in Iron.................................................................................. 195
7.1.2 The Iron–Carbon System............................................................................. 195
7.1.3 Plain Carbon Steels....................................................................................... 197
7.1.3.1 Normalized Steels......................................................................... 197
7.1.3.2 Quenched and Tempered Steels.................................................. 198
7.1.4 Cast Irons....................................................................................................... 199
7.2 Rusting......................................................................................................................... 200
7.2.1 Species in the Iron–Oxygen–Water System.............................................. 200
7.2.1.1 Iron(III) Oxides, Hydrous Oxides and Derivatives.................. 200
7.2.1.2 Iron(II) Oxides, Hydroxides and Derivatives............................ 201
7.2.1.3 Protective Value of Solid Species................................................ 202
7.2.2 Rusting in Aerated Water............................................................................ 202
7.2.2.1 Fresh Waters................................................................................... 202
Contents xi

7.2.2.2 Sea Waters...................................................................................... 203

7.2.2.3 Alkaline Waters............................................................................. 203
7.2.2.4 Suppression of Corrosion by Impressed Currents................... 204
7.2.3 Rusting in Air................................................................................................ 204
7.2.3.1 Rusting Due to Atmospheric Humidity.................................... 204
7.2.3.2 Rusting from Intermittent Wetting............................................ 205
7.2.4 Rusting of Cast Irons.................................................................................... 206
7.2.4.1 Gray Flake Irons............................................................................ 206
7.2.4.2 Other Irons..................................................................................... 207
7.3 The Oxidation of Iron and Steels............................................................................. 207
7.3.1 Crystallographic and Defect Structures of Oxides.................................. 207
7.3.2 Phase Equilibria in the Iron–Oxygen System........................................... 208
7.3.3 Application of Wagner’s Oxidation Mechanisms.................................... 209
7.3.3.1 Nature of Scales............................................................................. 209
7.3.3.2 Diffusing Species and Growth Interfaces.................................. 209
7.3.3.3 Oxidation Rates............................................................................. 210
7.3.4 Oxidation of Steels........................................................................................ 211
7.3.4.1 Effects of Alloying Elements and Impurities............................ 211
7.3.4.2 Influence on Metal Quality of Scales Formed during
Manufacture................................................................................... 212
7.3.4.3 Oxidation in Industrial Conditions............................................ 212
7.3.5 Oxidation and Growth of Cast Irons......................................................... 212
7.3.5.1 Internal Oxidation......................................................................... 213
7.3.5.2 Graphitization................................................................................ 213
Further Reading.................................................................................................................... 214

8 Stainless Steels..................................................................................................................... 215

8.1 Phase Equilibria......................................................................................................... 215
8.1.1 The Iron–Chromium System...................................................................... 216
8.1.2 Effects of Other Elements on the Iron–Chromium System.................... 217
8.1.2.1 Carbon............................................................................................. 217
8.1.2.2 Nickel.............................................................................................. 217
8.1.2.3 Nickel and Carbon Present Together......................................... 218
8.1.2.4 Molybdenum.................................................................................. 219
8.1.2.5 Other Elements.............................................................................. 219
8.1.3 Schaeffler Diagrams..................................................................................... 219
8.2 Commercial Stainless Steels..................................................................................... 221
8.2.1 Classification.................................................................................................. 221
8.2.2 Structures....................................................................................................... 221
8.2.2.1 Ferritic Steels.................................................................................. 221
8.2.2.2 Austenitic Steels............................................................................ 221
8.2.2.3 Martensitic Steels..........................................................................222
8.2.2.4 Duplex Steels..................................................................................223
8.2.2.5 Precipitation-Hardening Steels................................................... 223
8.3 Resistance to Aqueous Corrosion............................................................................223
8.3.1 Evaluation from Polarization Characteristics...........................................223
8.3.1.1 Relevance to Corrosion Resistance............................................. 223
8.3.1.2 Determination................................................................................ 224
8.3.1.3 Presentation.................................................................................... 227
xii Contents

8.3.1.4 Influence of the Environment...................................................... 228

8.3.1.5 Influence of Steel Composition and Condition......................... 229
8.3.2 A Chemical View of Passivity in Iron Chromium Alloys...................... 229
8.3.2.1 Oxidation States of Chromium and Related Equilibria.......... 229
8.3.2.2 Relation of Polarization Characteristics to Chromium
Chemistry....................................................................................... 231
8.3.3 Corrosion Characteristics of Stainless Steels............................................ 233
8.3.3.1 Corrosion Resistance in Acids..................................................... 233
8.3.3.2 Pitting Corrosion...........................................................................234
8.3.3.3 Crevice Corrosion.......................................................................... 237
8.3.3.4 Sensitization and Intergranular Corrosion............................... 237
8.3.3.5 Corrosion in Aggressive Chemical Environments................... 239
8.4 Resistance to Dry Oxidation..................................................................................... 239
8.5 Applications................................................................................................................ 240
8.5.1 Ferritic Steels................................................................................................. 241
8.5.2 Austenitic Steels............................................................................................ 241
8.5.2.1 Austenitic Steels without Molybdenum.................................... 241
8.5.2.2 Austenitic Steels with Molybdenum.......................................... 241
8.5.2.3 Austenitic Steels with Manganese Substitution....................... 242
8.5.3 Hardenable Steels......................................................................................... 242
8.5.4 Duplex Steels................................................................................................. 242
8.5.5 Oxidation-Resistant Steels........................................................................... 243
8.6 Applications of Cast Stainless Steels....................................................................... 243
Problems................................................................................................................................. 245
Further Reading.................................................................................................................... 247

9 Corrosion Resistance of Aluminium and Aluminium Alloys................................... 249

9.1 Physical Metallurgy of Some Standard Alloys...................................................... 249
9.1.1 Alloys Used without Heat Treatment........................................................ 250
9.1.1.1 Commercial Pure Aluminium Grades (AA 1XXX
Alloy Series)................................................................................... 250
9.1.1.2 Aluminium–Manganese Alloy AA 3003................................... 250
9.1.1.3 Aluminium–Magnesium Alloys (AA 5000 Series)................... 251
9.1.1.4 Aluminium–Magnesium–Manganese Alloy AA 3004............ 252
9.1.2 Heat-Treatable (Aging) Alloys..................................................................... 252
9.1.2.1 Aluminium–Copper–Magnesium Alloys (e.g., AA 2024)........ 253
9.1.2.2 Aluminium–Zinc–Magnesium Alloys (e.g., AA 7075)............. 253
9.1.2.3 Aluminium–Magnesium–Silicon Alloys (e.g., AA 6061).........254
9.1.2.4 Aluminium Alloys Containing Lithium...................................254
9.1.3 Casting Alloys...............................................................................................254
9.2 Corrosion Resistance................................................................................................. 255
9.2.1 The Aluminium–Oxygen–Water System.................................................. 255
9.2.1.1 Solid Species................................................................................... 256
9.2.1.2 Soluble Species............................................................................... 257
9.2.2 Corrosion Resistance of Pure Aluminium in Aqueous Media.............. 257
9.2.2.1 Passivation...................................................................................... 257
9.2.2.2 Corrosion Resistance in Natural Waters.................................... 258
9.2.2.3 Corrosion Resistance in Acidic and Alkaline Media............... 259
Contents xiii

9.2.3
Corrosion Resistance of Aluminium Alloys in Aqueous Media........... 259
9.2.3.1 Chemical Composition of the Metal........................................... 259
9.2.3.2 Structure Sensitivity..................................................................... 261
9.2.3.3 Stress-Corrosion Cracking........................................................... 262
9.2.3.4 Galvanically Stimulated Attacks................................................ 263
9.2.4 Corrosion Resistance of Aluminium and Its Alloys in Air.................... 263
9.2.4.1 Nature of Air-Formed Film......................................................... 263
9.2.4.2 Weathering..................................................................................... 263
9.2.5 Geometric Effects.......................................................................................... 264
9.2.5.1 Crevices........................................................................................... 264
9.2.5.2 Impingement, Cavitation and Erosion–Corrosion................... 264
9.2.6 Oxidation of Aluminium–Magnesium Alloys during Manufacture.........265
9.2.6.1 Enhanced Oxidation by Sulfur Pollution.................................. 265
9.2.6.2 Oxide Precursor of Magnesium Carbonate Films.................... 266
Further Reading.................................................................................................................... 267

10 Corrosion Resistance of Copper and Copper Alloys................................................... 269

10.1 Chemical Properties and Corrosion Behaviour of Pure Copper........................ 269
10.1.1 The Copper–Oxygen–Water System.......................................................... 271
10.1.2 Corrosion Resistance in Natural Environments...................................... 271
10.1.2.1 The Atmosphere............................................................................ 271
10.1.2.2 Natural Waters............................................................................... 272
10.1.2.3 Soils................................................................................................. 272
10.1.3 Water Supply and Circulation Systems..................................................... 273
10.1.3.1 Surface Films as Cathodic Collectors......................................... 273
10.1.3.2 Impingement Attack..................................................................... 273
10.1.3.3 Pitting.............................................................................................. 273
10.1.4 Stress-Related Corrosion Failure................................................................ 273
10.1.5 Corrosion of Associated Metals by Galvanic Stimulation...................... 274
10.2 Constitutions and Corrosion Behaviour of Copper Alloys................................. 274
10.2.1 Alloys Based on the Copper–Zinc System–Brasses................................. 274
10.2.1.1 Phase Equilibria for the Copper–Zinc Binary System............. 275
10.2.1.2 Formulation and Characteristics of Alloys................................ 276
10.2.1.3 Corrosion Resistance.................................................................... 277
10.2.2 Alloys Based on the Copper–Aluminium System................................... 278
10.2.2.1 Phase Equilibria for the Copper–Aluminium
Binary System................................................................................ 278
10.2.2.2 Formulation and Characteristics of Alloys................................ 278
10.2.2.3 Corrosion Resistance.................................................................... 280
10.2.3 Alloys Based on the Copper–Nickel System............................................. 282
10.2.3.1 Phase Equilibria for the Copper–Nickel Binary System......... 282
10.2.3.2 Formulation and Characteristics of Alloys................................ 282
10.2.3.3 Corrosion Resistance in Water.................................................... 283
10.2.4 Alloys Based on the Copper–Tin System.................................................. 283
10.2.4.1 Phase Equilibria for the Copper–Tin Binary System............... 283
10.2.4.2 Formulation and Characteristics of Alloys................................284
10.2.4.3 Corrosion Resistance....................................................................284
Further Reading.................................................................................................................... 285
xiv Contents

11 Corrosion Resistance of Nickel and Its Alloys.............................................................. 287

11.1 Chemical Properties and Corrosion Behaviour of Pure Nickel.......................... 287
11.1.1 The Nickel–Oxygen–Water System............................................................ 287
11.1.2 Corrosion Resistance in Natural Environments...................................... 288
11.1.2.1 The Natural Atmosphere............................................................. 288
11.1.2.2 Natural Waters............................................................................... 288
11.1.3 Corrosion Resistance in Neutral and Alkaline Media............................ 288
11.1.4 Corrosion Resistance in Acidic Media....................................................... 289
11.1.5 Non-Aqueous Media.................................................................................... 289
11.2 Constitutions and Corrosion Behaviour of Nickel Alloys................................... 290
11.2.1 Nickel Alloys for General Corrosion Resistance...................................... 291
11.2.1.1 Nickel–Copper Alloys (Monels).................................................. 291
11.2.1.2 Nickel–Chromium Alloys (Nichrome and Inconel)................. 295
11.2.1.3 Nickel Alloys Containing Molybdenum.................................... 296
11.2.2 Superalloys for Gas Turbine Components................................................ 298
11.2.2.1 Properties of Materials for Gas Turbines................................... 298
11.2.2.2 Design of Microstructures........................................................... 298
11.2.2.3 Alloy Range.................................................................................... 299

12 Corrosion Resistance of Titanium and Its Alloys......................................................... 301

12.1 Chemical Characteristics and Corrosion Behaviour of Pure Titanium............. 302
12.1.1 The Titanium–Water System....................................................................... 302
12.1.2 Corrosion Resistance.................................................................................... 302
12.1.2.1 Passivity.......................................................................................... 302
12.1.2.2 Stress-Related Corrosion.............................................................. 303
12.1.2.3 Titanium in Mixed Metal Systems.............................................. 303
12.1.2.4 Resistance to Natural Environments..........................................304
12.1.2.5 Resistance to Acids........................................................................304
12.2 Constitutions and Corrosion Behaviour of Titanium Alloys..............................306
12.2.1 Alloy Formulation........................................................................................306
12.2.2 Noble Metal Additions for Improved Resistance to
Non-Oxidizing Acids................................................................................... 306
12.3 Applications................................................................................................................308
12.3.1 Aerospace Applications...............................................................................308
12.3.2 Marine Applications.....................................................................................308
12.3.3 Representative Industrial Applications.....................................................308
12.3.3.1 Chemical and Related Process Plants........................................308
12.3.3.2 Bleaching and Bleaching Agents.................................................309
12.3.3.3 Oilfield Equipment........................................................................309
12.3.3.4 Anodes for Cathodic Protection..................................................309
12.3.3.5 Equipment for Metal Surface Treatments..................................309
12.3.4 Medical Applications................................................................................... 310
12.3.4.1 Titanium Alloy Joint Replacements............................................ 310
12.3.4.2 Other Titanium Implants and Prostheses................................. 311

13 Corrosion Resistance of Zinc............................................................................................ 313

13.1 Occurrence and Extraction....................................................................................... 313
13.1.1 Sources............................................................................................................ 313
13.1.2 Blast Furnace Reduction.............................................................................. 313
Contents xv

13.1.3 Electrolytic Extraction.................................................................................. 313

13.2 Structure and Properties........................................................................................... 314
13.2.1 Structure and Physical Properties.............................................................. 314
13.2.2 Chemical Properties..................................................................................... 314
13.2.2.1 Electron Configuration................................................................. 314
13.2.2.2 Passivation...................................................................................... 314
13.3 Applications................................................................................................................ 315
13.3.1 Surface Coatings on Steel............................................................................ 315
13.3.2 Sacrificial Anodes......................................................................................... 315
13.3.3 Batteries Based on the Leclanché Cell....................................................... 316
13.3.4 Diecastings..................................................................................................... 316
13.4 Corrosion Characteristics of Zinc............................................................................ 316
13.4.1 Corrosion in Aqueous Solution.................................................................. 316
13.4.2 Corrosion in Normal Atmospheres............................................................ 317
13.5 Cadmium.................................................................................................................... 317
Further Reading.................................................................................................................... 318

14 Corrosion Resistance of Magnesium and Its Alloys.................................................... 319

14.1 Physical Properties..................................................................................................... 319
14.1.1 Occurrence and Extraction.......................................................................... 319
14.2 Chemical Properties.................................................................................................. 319
14.3 Corrosion Resistance................................................................................................. 320
14.3.1 Corrosion Resistance in Aqueous Solution............................................... 320
14.3.2 Corrosion Resistance in Dry Oxidation..................................................... 321
14.4 Alloy Formulation...................................................................................................... 322
14.5 Canning for Nuclear Reactor Fuel........................................................................... 322
14.6 Stress-Corrosion Cracking........................................................................................ 322
14.6.1 Susceptible Alloys......................................................................................... 322
14.6.2 Mechanisms................................................................................................... 322
14.7 Magnesium Sacrificial Anodes................................................................................ 323
14.8 Protection of Magnesium by Coatings.................................................................... 323
14.8.1 Paint Systems................................................................................................. 324
14.8.2 Anodizing...................................................................................................... 324

15 Corrosion Resistance of Tin and Tin Alloys.................................................................. 325

15.1 Occurrence Extraction and Refining....................................................................... 325
15.2 Chemical Characteristics and Corrosion Resistance............................................ 325
15.2.1 Corrosion Resistance in Natural Environments...................................... 326
15.2.2 Applications................................................................................................... 326
15.2.2.1 Tin Coatings on Steel for Food Cans.......................................... 326
15.2.2.2 Soft Solders..................................................................................... 327
15.2.2.3 Lead-Free Solders.......................................................................... 327
15.2.3 Bearings.......................................................................................................... 327
15.2.4 Pure Tin and Pewter..................................................................................... 327

16 Corrosion Resistance of Lead............................................................................................ 329

16.1 Occurrence and Extraction....................................................................................... 329
16.2 Chemical Characteristics and Corrosion Behaviour............................................ 329
16.2.1 Chemical Characteristics............................................................................. 329
xvi Contents

16.2.2 Corrosion Resistance.................................................................................... 330

16.2.2.1 Corrosion Resistance in Air and Water...................................... 330
16.2.2.2 Corrosion Resistance in Acids..................................................... 330
16.2.2.3 Effects of Stress.............................................................................. 332
16.3 Applications................................................................................................................ 332
16.3.1 Lead Acid Batteries....................................................................................... 332
16.3.2 Equipment for Electrochemical Metal Finishing..................................... 333
16.3.2.1 Electrodeposition of Metals......................................................... 333
16.3.2.2 Anodizing Aluminium................................................................334
16.3.3 Roofing Materials..........................................................................................334

17 Corrosion Resistance of Zirconium and Hafnium....................................................... 335

17.1 Occurrence Extraction and Refining....................................................................... 335
17.2 Some Chemical Characteristics and Corrosion Behaviour.................................. 335
17.2.1 Corrosion Resistance.................................................................................... 336
17.2.1.1 Oxidation Mechanisms................................................................ 336
17.2.1.2 Passivity.......................................................................................... 337
17.2.1.3 Breakdown of Passivity................................................................ 338
17.3 Applications................................................................................................................ 338
17.3.1 Nuclear Applications.................................................................................... 338
17.3.2 Chemical, Industrial and Medical Applications...................................... 338

18 Corrosion Resistance of Beryllium.................................................................................. 339

18.1 Occurrence and Extraction....................................................................................... 339
18.1.1 Sources............................................................................................................ 339
18.1.2 Extraction of Raw Metal by Halide Routes............................................... 339
18.1.3 Purification Swarfing and Consolidation.................................................. 339
18.2 Characteristics of Commercially Pure Metal.........................................................340
18.2.1 Structure and Physical Properties..............................................................340
18.2.2 Nuclear Properties........................................................................................ 341
18.2.3 Chemical Properties and Corrosion Behaviour....................................... 341
18.2.3.1 Electron Configuration................................................................. 341
18.2.3.2 Chemical Characteristics............................................................. 341
18.2.3.3 Passivation by Surface Oxide Film.............................................342
18.2.3.4 Pitting at Local Cathodic Collectors...........................................342
18.2.3.5 Effects of Carbide Inclusions.......................................................343
18.3 Applications................................................................................................................344
18.3.1 Nuclear Reactors...........................................................................................344
18.3.1.1 Responses to Reactor Environments..........................................344
18.3.1.2 Integrity of Beryllium as a Structural Material........................345
18.3.2 Applications Exploiting High Strength to Weight Ratio.........................345

19 Corrosion Resistance of Uranium.................................................................................... 347

19.1 Occurrence and Extraction of the Natural Metal.................................................. 347
19.2 Uranium Metallurgy and Chemistry...................................................................... 347
19.2.1 Metallurgy..................................................................................................... 347
19.2.2 Chemical Characteristics.............................................................................348
19.3 Corrosion in Water and Steam................................................................................. 349
19.3.1 Corrosion Products....................................................................................... 349
Contents xvii

19.3.2 Kinetics........................................................................................................... 350

19.3.3 Effects of Hydrogen Absorption................................................................. 350
19.4 Oxidation..................................................................................................................... 350
19.4.1 Uranium–Oxygen Phase Equilibria........................................................... 350
19.4.2 Critical Review of Uranium Oxide Structures......................................... 352
19.4.3 Application of Critical Review to Oxidation Kinetics............................. 352
19.4.4 Effects of Alloying Elements on Oxidation Kinetics............................... 353

20 Cathodic Protection............................................................................................................. 355

20.1 Principles..................................................................................................................... 355
20.2 Buried Pipelines and Distribution Systems........................................................... 357
20.2.1 Protection by Impressed Current............................................................... 357
20.2.1.1 Schemes for New Buried Pipelines............................................ 359
20.2.1.2 Retrofitting to Existing Buried Pipelines................................... 359
20.2.1.3 Anodes and Groundbeds for Impressed Current.................... 359
20.2.2 Protection by Sacrificial Anodes................................................................. 360
20.3 Cathodic Protection in Open Waters....................................................................... 361
20.3.1 Protection of Ships’ Hulls............................................................................ 362
20.3.1.1 Protection of Hulls by Impressed Current................................ 362
20.3.1.2 Protection of Hulls by Sacrificial Anodes.................................. 363
20.3.1.3 Protection of Internal Hull Components................................... 363
20.3.2 Protection of Coastal and Offshore Installations..................................... 363
20.4 Side Reactions and Overprotection.........................................................................364
20.5 Measuring Instruments............................................................................................ 365
20.5.1 Measurement of Potentials.......................................................................... 365
20.5.1.1 Buried Pipes and Utilities............................................................ 365
20.5.1.2 Immersed Structures.................................................................... 366
20.5.2 Measurement of Soil Resistivities............................................................... 366
Further Reading.................................................................................................................... 367

21 Corrosion and Corrosion Control in Aviation............................................................... 369

21.1 Airframes.................................................................................................................... 369
21.1.1 Materials of Construction............................................................................ 369
21.1.2 Corrosion and Protection of Airframes..................................................... 370
21.1.2.1 Aluminium Alloys........................................................................ 370
21.1.2.2 Titanium Alloys............................................................................. 371
21.1.2.3 Other Metals.................................................................................. 372
21.1.3 Environmentally Sensitive Cracking......................................................... 372
21.1.3.1 Fatigue............................................................................................. 372
21.1.3.2 Stress-Corrosion Cracking........................................................... 372
21.1.4 Systematic Assessment for Corrosion Control......................................... 373
21.2 Gas Turbine Engines.................................................................................................. 374
21.2.1 Engine Operation.......................................................................................... 374
21.2.2 Application and Performance of Nickel Alloys........................................ 375
21.2.2.1 Oxidation in Unpolluted Combustion Products....................... 375
21.2.2.2 Aluminizing for Oxidation Resistance...................................... 376
21.2.2.3 Hot Corrosion and Sulfidation.................................................... 376
21.2.3 Engine Environments................................................................................... 377
21.2.3.1 Factors Related to Engine Operation.......................................... 377
xviii Contents

21.2.3.2 Flight Pattern Factors.................................................................... 378

21.2.3.3 Fatigue............................................................................................. 379
21.2.4 Alloy Selection.............................................................................................. 379
21.2.4.1 Turbine Blades............................................................................... 379
21.2.4.2 Turbine Discs................................................................................. 380
21.2.4.3 Combustion Chambers................................................................. 380
21.2.4.4 Compressor Assemblies............................................................... 380
21.2.4.5 Cool Components.......................................................................... 380
Further Reading.................................................................................................................... 381

22 Corrosion Control in Automobile Manufacture........................................................... 383

22.1 Overview..................................................................................................................... 383
22.2 Corrosion Protection for Automobile Bodies......................................................... 383
22.2.1 Design Considerations................................................................................. 383
22.2.1.1 Front and Side Panels...................................................................384
22.2.1.2 Wheel Arches.................................................................................384
22.2.1.3 Joints................................................................................................384
22.2.1.4 Rainways........................................................................................384
22.2.2 Overview of Paint Shop Operations..........................................................384
22.2.3 Cleaning and Pretreatment of Body Shells............................................... 385
22.2.4 Phosphating................................................................................................... 385
22.2.5 Application of Paint...................................................................................... 387
22.2.5.1 Primer Coat and Sealing.............................................................. 387
22.2.5.2 Undercoating Colour and Gloss Coats....................................... 388
22.2.5.3 Supplementary Protection........................................................... 388
22.2.6 Whole Body Testing...................................................................................... 388
22.3 Corrosion Protection for Engines............................................................................ 389
22.3.1 Exhaust Systems............................................................................................ 389
22.3.2 Cooling Systems............................................................................................ 389
22.3.3 Moving Parts................................................................................................. 389
22.4 Bright Trim.................................................................................................................. 390
22.4.1 Electrodeposited Nickel Chromium Systems........................................... 391
22.4.2 Anodized Aluminium................................................................................. 391
Further Reading.................................................................................................................... 392

23 Corrosion Control in Food Processing and Distribution............................................ 393

23.1 General Considerations............................................................................................. 393
23.1.1 Public Health................................................................................................. 393
23.1.1.1 Control of Hygiene at Food/Metal Contacts............................. 393
23.1.2 Food Product Environments....................................................................... 394
23.1.2.1 Bacteria in the Environment........................................................ 394
23.1.2.2 Emulsified Environments............................................................ 395
23.1.2.3 Interaction between Inorganic and Organic Solutes................ 395
23.1.2.4 Practical Aspects of Corrosion Control...................................... 396
23.2 Production of Tinplate for Food Cans..................................................................... 396
23.2.1 Historical........................................................................................................ 396
23.2.2 Modern Tinplate Cans.................................................................................. 396
23.2.2.1 Electrodeposition, Flow Melting and Passivation.................... 397
23.2.2.2 Three-Piece Cans........................................................................... 397
Contents xix

23.2.2.3 Draw/Redraw Cans...................................................................... 397

23.2.2.4 Draw/Wall-Iron Cans................................................................... 397
23.2.3 Tin-Free Steel for Food Packaging.............................................................. 398
23.3 Dairy Industries......................................................................................................... 398
23.3.1 Milk and Its Derivatives.............................................................................. 398
23.3.1.1 Constitution................................................................................... 398
23.3.1.2 Processing....................................................................................... 399
23.3.2 Materials Used in the Dairy Industry....................................................... 401
23.3.2.1 Surfaces in Contact with the Product......................................... 401
23.3.2.2 Surfaces Not in Contact with the Product................................. 402
23.4 Brewing....................................................................................................................... 402
23.4.1 The Brewing Process.................................................................................... 402
23.4.2 Materials Used for Brewing Plants............................................................404
23.4.2.1 General Corrosion Resistance.....................................................404
23.4.2.2 Stress-Corrosion Cracking...........................................................404
23.4.2.3 Biologically Promoted Corrosion in
Spent Grain Hoppers....................................................................405
23.4.2.4 Cleaning and Sterilization........................................................... 405
23.4.3 Beer Barrels, Casks and Kegs...................................................................... 405
23.4.3.1 Historical........................................................................................ 405
23.4.3.2 Design............................................................................................. 406
23.4.3.3 Materials......................................................................................... 407
Further Reading....................................................................................................................408

24 Control of Corrosion in Building Construction............................................................ 409

24.1 Introduction................................................................................................................ 409
24.2 Structures.................................................................................................................... 410
24.2.1 Steel Bar for Reinforced Concrete Frames................................................. 410
24.2.1.1 Reinforced Concrete..................................................................... 410
24.2.1.2 Chemical Environment in Concrete........................................... 410
24.2.1.3 Protective Measures Applied to the Concrete.......................... 411
24.2.1.4 Protective Measures Applied to the Steel.................................. 412
24.2.1.5 Stress-Corrosion Cracking of Pre-Stressed
Reinforcement Bar......................................................................... 413
24.2.2 Steel Frames................................................................................................... 413
24.2.2.1 Design............................................................................................. 414
24.2.2.2 Protection....................................................................................... 414
24.2.3 Traditional Structures.................................................................................. 414
24.2.3.1 Wall Ties......................................................................................... 414
24.2.3.2 Rainwater Goods........................................................................... 415
24.3 Cladding...................................................................................................................... 415
24.3.1 Reinforced Concrete Panels......................................................................... 415
24.3.2 Aluminium Alloy Panels............................................................................. 415
24.4 Metal Roofs, Siding and Flashing............................................................................ 416
24.4.1 Self-Supporting Roofs and Siding.............................................................. 416
24.4.2 Fully Supported Roofs and Flashings....................................................... 417
24.5 Plumbing and Central Heating Installations......................................................... 417
24.5.1 Pipes................................................................................................................ 417
24.5.1.1 Galvanized Steel............................................................................ 417
xx Contents

24.5.2 Tanks............................................................................................................... 418

24.5.3 Joints............................................................................................................... 418
24.5.4 Central Heating Circuits.............................................................................. 419
24.6 Corrosion of Metals in Timber................................................................................. 419
24.6.1 Contact Corrosion......................................................................................... 419
24.6.2 Corrosion by Vapours from Wood............................................................. 420
24.7 Application of Stainless Steels in Leisure Pool Buildings.................................... 420
24.7.1 Corrosion Damage........................................................................................ 421
24.7.1.1 Safety-Critical Damage by Stress-Corrosion Cracking........... 421
24.7.1.2 Area Damage................................................................................. 421
24.7.2 Control............................................................................................................422
Further Reading....................................................................................................................422

25 Corrosion Control in Marine Environments.................................................................423

25.1 The Nature of Marine Environments......................................................................423
25.1.1 The Sea...........................................................................................................423
25.1.1.1 Composition of Seawaters............................................................423
25.1.1.2 Temperature................................................................................... 424
25.1.1.3 Dynamics........................................................................................ 424
25.1.1.4 Biology............................................................................................425
25.1.2 Marine Atmospheres....................................................................................425
25.2 Ships.............................................................................................................................425
25.2.1 Paints for Steel Hulls....................................................................................425
25.2.1.1 Ships’ Bottoms............................................................................... 426
25.2.1.2 Ships’ Tops and Superstructures................................................ 426
25.2.1.3 Waterline Zones............................................................................. 427
25.2.1.4 Interior Surfaces............................................................................ 427
25.2.1.5 Surface Preparation and Application......................................... 428
25.2.2 Aluminium Alloy Superstructures............................................................ 429
25.2.3 Propellers.......................................................................................................430
25.2.4 Marine Gas Turbine Engines.......................................................................430
25.2.5 Miscellaneous Components........................................................................ 431
25.2.6 Heat Exchangers........................................................................................... 431
25.3 Offshore Platforms..................................................................................................... 431
25.3.1 Structures....................................................................................................... 432
25.3.2 Systems Using Seawater.............................................................................. 432
25.3.2.1 Pipes for Seawater......................................................................... 432
25.3.2.2 Seawater Pumps............................................................................ 433
25.3.2.3 Valves for Seawater....................................................................... 433
25.3.3 Sour Service Environments.........................................................................433
25.3.4 Submerged Oil and Gas Pipelines..............................................................434
25.3.5 Submerged Fasteners and Fittings.............................................................434
Further Reading....................................................................................................................434

26 Corrosion Control for Fossil Fuel Boilers for Steam Raising..................................... 435
26.1 Waterside Corrosion Control.................................................................................... 435
26.1.1 Passivation of Iron in Superheated Water and Steam.............................. 436
26.1.2 Surface Preparation of Steel for Passivation.............................................. 437
26.1.3 Treatment and Control of Boiler Water...................................................... 437
Contents xxi

26.1.3.1 Control of pH................................................................................. 438

26.1.3.2 Removal of Dissolved Oxygen.................................................... 438
26.1.3.3 Elimination of the Precursors of Calcareous Scale.................. 439
26.1.3.4 Monitoring for Contaminants..................................................... 439
26.1.3.5 Use of Inhibitors............................................................................ 439
26.1.4 Alloys for High Temperature Superheater Tubes.................................... 439
26.2 Fireside Corrosion Control.......................................................................................440
26.2.1 Fuels................................................................................................................440
26.2.1.1 Coals and Oils................................................................................440
26.2.1.2 Natural Gas.................................................................................... 441
26.2.2 Fireside Environments................................................................................. 441
26.2.2.1 Combustion Chamber Atmospheres.......................................... 441
26.2.2.2 Ionic Liquid Environments.......................................................... 441
26.2.3 Corrosion Control of Principal Components............................................442
26.2.3.1 Water Evaporation Tubes.............................................................442
26.2.4 Superheater Tubes.........................................................................................442
26.2.4.1 Combustion Chamber..................................................................442
26.2.4.2 Downstream Ancillary Equipment............................................443
26.2.4.3 Care of Fireside Surfaces during Idle Periods...........................443

27 Some Corrosion Issues in Nuclear Engineering...........................................................445

27.1 Overview.....................................................................................................................445
27.2 Fusion...........................................................................................................................446
27.3 Fission..........................................................................................................................446
27.3.1 Pressurized Water Reactors (PWRs).......................................................... 447
27.3.1.1 The Reactor Core........................................................................... 447
27.3.1.2 The Steam Generator.................................................................... 447
27.3.1.3 Water Treatment............................................................................ 450
27.3.1.4 Corrosion and Corrosion Control............................................... 451
27.3.1.5 Corrosion in the Primary Water Circuit.................................... 451
27.3.1.6 Corrosion in the Secondary Water Circuit................................ 451
27.3.2 Boiling Water Reactors (BWRs)................................................................... 453
27.3.2.1 Noble Metal Chemical Addition.................................................454
27.3.2.2 Zinc Addition.................................................................................454
27.3.3 Breakaway Oxidation................................................................................... 455
27.3.3.1 Breakaway Oxidation of Zirconium Alloys by Steam............. 455
27.3.3.2 Breakaway Oxidation in Steels.................................................... 455
27.3.4 Radiation-Induced Creep and Oxidation.................................................. 456
27.4 Nuclear Propulsion.................................................................................................... 456
27.5 Regulated Materials................................................................................................... 457
27.6 Containment, Decommissioning and Disposal.................................................... 457
27.7 Summary..................................................................................................................... 458
Further Reading.................................................................................................................... 458

28 Oilfield Corrosion................................................................................................................ 459

28.1 Overview..................................................................................................................... 459
28.1.1 Terminology.................................................................................................. 460
28.1.1.1 Sectors............................................................................................. 460
28.1.1.2 Oil Types......................................................................................... 460
xxii Contents

28.1.1.3 Location Descriptions and Equipment...................................... 460

28.2 Oilfield Chemistry..................................................................................................... 461
28.2.1 Chemical Modelling..................................................................................... 462
28.3 Materials Issues..........................................................................................................463
28.3.1 Marine Applications.....................................................................................463
28.3.2 Corrosion-Resistant Alloys..........................................................................463
28.3.3 Oilfield Corrosion Control Phenomena.....................................................464
28.3.3.1 Carbon Dioxide Corrosion...........................................................464
28.3.3.2 Wet H2S Cracking..........................................................................464
28.3.3.3 Top of Line Corrosion................................................................... 465
28.3.3.4 Drill Mud........................................................................................ 465
28.3.3.5 Microbial Corrosion...................................................................... 465
28.3.3.6 Cathodic Protection...................................................................... 465
28.3.3.7 Corrosion under Insulation......................................................... 465
28.4 Inhibitors..................................................................................................................... 465
28.4.1 Batch Application.......................................................................................... 466
28.4.2 Continuous Application............................................................................... 466
28.5 Summary..................................................................................................................... 466
Further Reading.................................................................................................................... 466

29 Principles of Corrosion Testing........................................................................................ 467

29.1 Accelerated Tests........................................................................................................ 467
29.2 Exposure Tests............................................................................................................ 468
29.3 Pilot Tests.................................................................................................................... 469
29.4 Stress-Enhanced Corrosion Tests............................................................................ 469
29.4.1 Tests for SCC.................................................................................................. 469
29.4.2 Corrosion Fatigue Tests................................................................................ 469
29.4.3 Tests for Erosion–Corrosion Cavitation and Impingement.................... 470
29.5 Tests for Resistance to Thermal Oxidation............................................................. 470
29.5.1 Thermogravimetric Measurements........................................................... 470
29.5.2 Exposure and Pilot Tests.............................................................................. 470
Further Reading.................................................................................................................... 471

30 Prediction of Corrosion Failures...................................................................................... 473

30.1 Overview..................................................................................................................... 473
30.1.1 Engineering Performance and Economics................................................ 476
30.1.2 Laboratory Tests and Standards................................................................. 477
30.1.3 Redesign, Misdesign and Rectification..................................................... 477
30.1.3.1 Quality Control, Quality Management, Certification and
Other Data...................................................................................... 479
30.1.3.2 Knowledge-Based Systems..........................................................480
30.1.3.3 Competences.................................................................................. 481
30.1.4 Systems Assessment..................................................................................... 485
30.1.4.1 Systems Engineering Tools.......................................................... 488
30.1.4.2 Design Hierarchy.......................................................................... 489
30.1.4.3 The OODA Loop and Refining of Options for Corrosion
Prediction....................................................................................... 490
30.1.4.4 Availability, Reliability and Maintainability............................ 493
30.2 Mechanisms................................................................................................................ 493
Contents xxiii

30.2.1 General Mechanistic Principles.................................................................. 493

30.2.2 Depassivation and Electrochemistry......................................................... 494
30.2.2.1 Depassivation................................................................................. 494
30.2.2.2 Implied Consequences of the Tafel and Butler–Volmer
Equations........................................................................................ 494
30.2.3 Stainless Steels.............................................................................................. 495
30.2.3.1 General Features of Pitting of Chromium Alloys.................... 495
30.2.3.2 The Chemical Approach to Passivity......................................... 497
30.2.3.3 Calculation of the Percentage of Chromium to Passivate
Stainless Steels............................................................................... 499
30.2.3.4 Depassivation by Replacement Ligands.................................... 502
30.2.3.5 The Fundamental Evidence.........................................................504
30.2.3.6 Dependence of the Initial Reaction on Species Activity.......... 509
30.2.3.7 Other Phenomena......................................................................... 510
30.2.3.8 Mechanism Summary.................................................................. 516
30.2.4 Pitting of Commercial Grade Aluminium................................................ 519
30.2.4.1 Initiation......................................................................................... 520
30.2.4.2 Propagation Kinetics..................................................................... 521
30.2.4.3 Summary........................................................................................ 522
30.2.5 Low Temperature Thermal Oxidation....................................................... 523
30.3 Physical and Biological Vectors................................................................................ 523
30.3.1 The Intervention of Stress............................................................................ 523
30.3.2 Biological Vectors.......................................................................................... 524
30.3.2.1 Microbial-Induced Corrosion...................................................... 524
30.3.2.2 Ecology............................................................................................ 525
30.3.2.3 Environmental Impact Assessments.......................................... 526
30.4 Statistics....................................................................................................................... 527
30.4.1 Trials and Tests.............................................................................................. 527
30.4.1.1 Weibull Distribution and Truncated Data................................. 530
30.4.1.2 Elephant Tests, Burn-In and Burn-Out...................................... 530
30.4.2 In-Service Considerations............................................................................ 531
30.5 Kinetics, Modelling and Prediction........................................................................ 531
30.5.1 Electrical Models........................................................................................... 531
30.5.1.1 Initiation......................................................................................... 532
30.5.1.2 Propagation.................................................................................... 532
30.5.2 Chemical Modelling..................................................................................... 533
30.5.2.1 General Points................................................................................ 533
30.5.2.2 Simple Tools................................................................................... 533
30.5.2.3 More Complex Models.................................................................534
30.6 Epilogue....................................................................................................................... 535
Further Reading.................................................................................................................... 536
Index.............................................................................................................................................. 539
Preface to the Third Edition

In earlier editions of this book, corrosion issues were considered within a coherent
­framework of chemistry, physics and metallurgy. Guided by this information, corrosion
control of selected metals was evaluated in representative technologies according to public
safety and economic factors as well as technical feasibility.
In this third edition, the scope is enlarged and diversified. There are chapters on the
manufacture, structures, properties and corrosion resistance of aluminium, copper, nickel,
titanium, iron, magnesium, zinc, tin, lead, zirconium, hafnium, beryllium, uranium and
their alloys and strategies for applying them correctly and economically.
The extended range of technologies now includes aviation, automobile manufacture,
food processing and distribution, building construction, marine environments, fossil fuel
fired boilers, oilfield operations and nuclear topics. Finally, some of the various ways of
corrosion testing and prediction are addressed.

xxv
Authors

David E.J. Talbot (1926–2016), PhD, graduated with a BSc

and an MSc from the University of Wales and a PhD from
Brunel University for research on gas–metal equilibria.
From 1949 to 1966, he was employed at the research labora-
tories of the British Aluminium Company Ltd., contributing
to research promoting the development of manufacturing
­processes and to customer service. From 1966 to 1994, he
taught courses on corrosion and other aspects of chemical
metallurgy at Brunel University and maintained an active
interest in research and development, mainly in collabora-
tion with manufacturing industries in the United Kingdom
and the United States. He was a member of the Institute of
Materials and had chartered engineer status; he served as a
member of the council of the London Metallurgical Society. Dr. Talbot wrote many papers
on the chemical aspects of metallurgy, a review on metal–hydrogen systems in International
Metallurgical Reviews, and a section on gas–metal systems in Smithells Reference Book.

James D.R. Talbot, PhD, graduated with a BSc ARCS from Imperial College, London, and
earned an MSc from Brunel University. He earned a PhD from the University of Reading
for research on the physical chemistry of aqueous solutions and its application to natural
waters. Dr. Talbot worked at the River Laboratory of the Institute of Freshwater Ecology,
Dorset, United Kingdom, where he assessed and predicted physical chemical changes
occurring in river management. He has written papers on the speciation of solutes in
natural waters. From 2000 to 2006, he was a lecturer in materials research chemistry at
Cranfield University in the United Kingdom, where he specialized in the physicochemical
aspects of corrosion, polymer science and process science. He is presently a chemist with
interests in species-specific corrosion mechanisms. Dr. Talbot is a current member of the
Structure and Properties of Materials Committee of the Institute of Metals, Minerals and
Mining. He has published in the fields of corrosion, polymer chemistry, solution chemistry
and the chemistry of natural waters.

xxvii
Another random document with
no related content on Scribd:
 ¹⁵And Hilkiah answered and said to Shaphan
the scribe, I have found the book of the law in
the house of the Lord. And Hilkiah delivered
the book to Shaphan. ¹⁶And Shaphan carried
the book to the king, and moreover brought
the king word again, saying, All that was
committed to thy servants, they do it. ¹⁷And
they have emptied out ¹ the money that was
found in the house of the Lord, and have
delivered it into the hand of the overseers, and
into the hand of the workmen.
¹ Or, poured out.

15. answered and said] For the use of “answer” where no

question had been asked compare xxix. 31, note.

¹⁸And Shaphan the scribe told the king,

saying, Hilkiah the priest hath delivered me a
book. And Shaphan read therein before the
king.
18. And Shaphan read therein] Contrast 2 Kings, “And Shaphan
read it,” implying that he read the whole book, which of course was a
simple matter, if it consisted of the nucleus of Deuteronomy (see
note, verse 14). The Chronicler, however, believing the book to have
been the whole Pentateuch, could not suppose that the whole was
read to the king, and accordingly he writes therein in place of it.

¹⁹And it came to pass, when the king had

heard the words of the law, that he rent his
 clothes.
19. rent his clothes] A sign of grief. “Clothes” is in the plural
because both inner and outer garments are meant. See Ezra ix. 3
(with Ryle’s note).

²⁰And the king commanded Hilkiah, and

Ahikam the son of Shaphan, and Abdon the
son of Micah ¹, and Shaphan the scribe, and
Asaiah the king’s servant, saying,
¹ In 2 Kings xxii. 12, Achbor the son of Micaiah.

20. Ahikam the son of Shaphan] Compare Jeremiah xxvi. 24, xl.
5.

Abdon the son of Micah] In 2 Kings “Achbor the son of Micaiah.”

²¹Go ye, inquire of the Lord for me, and for

them that are left in Israel and in Judah,
concerning the words of the book that is
found: for great is the wrath of the Lord that is
poured out upon us, because our fathers have
not kept the word of the Lord, to do according
unto all that is written in this book.
21. for them that are left in Israel] Not in 2 Kings The Chronicler
likes to mention the remnants of the northern tribes, as in verses 6,
9.

that is poured out upon us] In 2 Kings “that is kindled against us,”
so LXX. ἐκκέκαυται. Compare verse 25.
 ²²So Hilkiah, and they whom the king had
commanded, went to Huldah the prophetess,
the wife of Shallum the son of Tokhath ¹, the
son of Hasrah ², keeper of the wardrobe; (now
she dwelt in Jerusalem in the second
quarter ³;) and they spake to her to that effect.
²³And she said unto them, Thus saith the
Lord, the God of Israel: Tell ye the man that
sent you unto me,
¹ In 2 Kings xxii. 14, Tikvah.

² In 2 Kings xxii. 14, Harhas. ³ Hebrew Mishneh.

22. had commanded] These words, which are obviously required,

are not in the Hebrew: the verb āmar has fallen out of the text by
some accident.

the prophetess] This title is given to Miriam (Exodus xv. 20),

Deborah (Judges iv. 4), Anna (Luke ii. 36); compare also Nehemiah
vi. 14; Revelation ii. 20.

Tokhath] In 2 Kings Tikvah.

Hasrah] In 2 Kings Harhas.

keeper of the wardrobe] Literally “keeper of the garments.” The

Hebrew word for garments (bĕgādim]) is applied to a king’s robes
(xviii. 29), to a high-priest’s vestments (Exodus xxviii. 2, 4), and to
clothes in general; it is therefore not easy to say what office precisely
is here referred to. Perhaps the garments here meant were
ecclesiastical and not royal. There is ample evidence that ancient
temples possessed a store of ceremonial garments for the use not
only of the worshippers but also of the images, compare 2 Kings x.
22, and generally the Encyclopedia Britannica¹¹ s.v. costume, pp.
230a, 231b. As early as the VIth dynasty an Egyptian priest is
mentioned as “master of the wardrobe.”

in the second quarter] Or, in the second division. Compare

Zephaniah i. 10. The physical configuration of ancient Jerusalem
was such that it might naturally be regarded as divided into two
districts, the eastern and western, with the valley of the Tyropœon
between. Compare Nehemiah iii. 9, 12, and also Nehemiah xi. 9
(with Ryle’s note on second over the city, which should probably be
rendered over the second part of the city).

²⁴Thus saith the Lord, Behold, I will bring evil

upon this place, and upon the inhabitants
thereof, even all the curses that are written in
the book which they have read before the king
of Judah: ²⁵because they have forsaken me,
and have burned incense unto other gods,
that they might provoke me to anger with all
the works of their hands; therefore is my wrath
poured out upon this place, and it shall not be
quenched.
24. all the curses] Deuteronomy xxvii. 15‒26, xxviii. 15‒68.

²⁶But unto the king of Judah, who sent you to

inquire of the Lord, thus shall ye say to him,
Thus saith the Lord, the God of Israel: As
touching the words which thou hast heard,
²⁷because thine heart was tender, and thou
didst humble thyself before God, when thou
heardest his words against this place, and
 against the inhabitants thereof, and hast
humbled thyself before me, and hast rent thy
clothes, and wept before me; I also have
heard thee, saith the Lord.
26. As touching the words which thou hast heard, because thine
heart] Read perhaps, Inasmuch as thou hast heard my words,
and thine heart. There is some slight flaw in the Hebrew text.

²⁸Behold, I will gather thee to thy fathers, and

thou shalt be gathered to thy grave in peace,
neither shall thine eyes see all the evil that I
will bring upon this place, and upon the
inhabitants thereof. And they brought the king
word again.
28. thou shalt be gathered to thy grave in peace] So also in 2
Kings But in point of fact Josiah met with a violent death, being slain
by Neco, king of Egypt, according both to Kings (2 Kings xxiii. 29)
and Chronicles (2 Chronicles xxxv. 23 f.). From the contradiction
between this prediction and the event, we may infer that in the
prophecy of Huldah we have an old and reliable tradition, which
obviously must have been made before the death of Josiah. That the
contradiction was allowed to stand in Kings is not perhaps surprising,
but it is remarkable in the Chronicler’s narrative. Not only does the
idea of a genuine prophecy failing to come true run counter to his
fixed principles, but (judging from many definite instances as well as
from the whole tone of his history) the tradition that a king so pious
from the start to the finish of his reign should meet his death in a
disastrous battle must have seemed to him well-nigh incredible. The
fact remains that he has allowed the tradition to stand, but it is
certainly surprising.
 neither shall thine eyes see] Compare the similar promise made
to Ahab (1 Kings xxi. 29).

29‒33 (= 2 Kings xxiii. 1‒3).

The Renewal of the Covenant with Jehovah.

This renewal of the covenant should be compared with the

passage describing Hezekiah’s great service of atonement for the
breach of the covenant (xxix. 20 ff.).

²⁹Then the king sent and gathered together

all the elders of Judah and Jerusalem. ³⁰And
the king went up to the house of the Lord,
and all the men of Judah and the inhabitants
of Jerusalem, and the priests, and the Levites,
and all the people, both great and small: and
he read in their ears all the words of the book
of the covenant that was found in the house of
the Lord.
30. the Levites] In 2 Kings “the prophets.”

³¹And the king stood in his place, and made a

covenant before the Lord, to walk after the
Lord, and to keep his commandments, and
his testimonies, and his statutes, with all his
heart, and with all his soul, to perform the
words of the covenant that were written in this
book. ³²And he caused all that were found in
Jerusalem and Benjamin to stand to it. And
 the inhabitants of Jerusalem did according to
the covenant of God, the God of their fathers.
31. to walk after the Lord] Compare Deuteronomy x. 12, 13.

³³And Josiah took away all the abominations

out of all the countries that pertained to the
children of Israel, and made all that were
found in Israel to serve, even to serve the
Lord their God. All his days they departed not
from following the Lord, the God of their
fathers.
33. And Josiah took away] Compare verses 3‒7.

all that were found in Israel] i.e. the remnant of the northern
tribes, compare verse 21.

All his days] Contrast the evil record of his son Jehoiakim, xxxvi.
5‒8.

Additional Note on verse 14.

Hilkiah the priest found the book of the law of the Lord] This
remarkable statement has proved to be a fruitful subject of
discussion. What precisely is meant by “the book of the law” said to
have been found by Hilkiah in the Temple? It is essential to
distinguish between the answer which the Chronicler would have
given to this question and the conclusions reached by an
independent survey of the problem. (1) Undoubtedly the Chronicler
supposed “the book of the law” to be the whole Pentateuch, since he
believed that the entire Law existed as it now is from the time of
Moses. The argument against his view is obvious to us at the
present time. Beside the practical objection of the impossibility of
reading the whole Pentateuchal Law twice in succession to different
persons on the same day (2 Kings xxii. 8, 10)—a difficulty which
perhaps the Chronicler himself perceived and sought to avoid, see
note on verse 18,—there is the overwhelming testimony of the
general evidence that a large part of the Pentateuch in its final form,
with which the Chronicler was familiar, is of post-exilic date. His
Pentateuch was quite certainly not “the book” found by Hilkiah. (2) It
is extremely interesting to observe that the first step towards the
judgement of modern criticism was taken at a very early date and by
certain of the Christian Fathers—Jerome, Procopius of Gaza,
Chrysostom—who put forward the view that the book in question
was not the whole Pentateuch but only the Book of Deuteronomy.
[For the details the student must be referred to articles in the
Zeitschrift für alttestamentliche Wissenschaft, 1902, pp. 170 f., 312
f., and the Journal of Biblical Literature, 1903, p. 50.] This view, first
developed scientifically by De Wette, gained eventually a very wide
acceptance amongst scholars. Stress is laid upon the resemblance
between the reforms ascribed to Josiah and the exhortations and
injunctions of Deuteronomy, particularly as regards the restriction of
sacrificial worship to one sanctuary (i.e. Jerusalem; compare
Deuteronomy xii. 10‒14). For the evidence the student may consult
Chapman, Introduction to the Pentateuch, pp. 135‒146, especially
pp. 142‒145 (in this series); or Driver, Deuteronomy (International
Critical Commentaries), pp. xliv ff. (3) Further, internal consideration
of the Book of Deuteronomy has led to the conclusion that it cannot
all date from the time of Josiah: and thus it is now generally held that
Hilkiah’s “book of the law” was not the final form of Deuteronomy, but
only the nucleus of that Book—probably chapters v.‒xxvi. and xxviii.,
or xii.‒xxvi. and xxviii., or even certain passages from those chapters
(see Chapman, Introduction to the Pentateuch, pp. 144, 145; or
Driver, Deuteronomy, pp. lxv ff.). (4) Finally, there are grounds for
doubting whether any part of Deuteronomy can be dated from the
time of Josiah. It is suggested that the Deuteronomic code is not
earlier than Jeremiah but later. Although this view does not yet
command general acceptance, it is fair to insist that it rests upon
evidence which cannot be so lightly set aside as is occasionally
supposed. The student may conveniently refer to remarks by R. H.
Kennett in the Encyclopaedia of Religion and Ethics, vol. vii., s.v.
Israel p. 447, and to the references there given, especially the
Journal of Theological Studies, VII. [1906], pp. 481 ff. If
Deuteronomy be later than the time of Josiah, what then can we
suppose this “book of the law” (sēpher hattōrah) to have been; for
there is no reason to question the accuracy of the tradition that some
impressive writing was discovered in the Temple? The answer will be
—in all probability—some scroll of prophetic teaching, in which the
abuses of worship (perhaps in Manasseh’s reign) and in particular
the corruptions of the country “high places” were searchingly
denounced and an appeal made for reform. Since at that date the
term tōrah was applicable to prophetic teaching as well as to legal
instruction, such a work would be known as “a book of tōrah.” It is
not a very serious objection that the text here and in Kings reads “the
book of the law (hattōrah),” partly because a peculiarity of Hebrew
grammar would still allow the translation “a book of tōrah,” partly
because the introduction of the definite article into the text would be
most natural, so soon as it came to be thought that the phrase
referred to Deuteronomy or the Pentateuch. We may summarise as
follows:—To the Chronicler “the book of the law” signified the whole
Pentateuch in its final form; to the compilers or editors of Kings (the
Chronicler’s source), who probably wrote at the “Deuteronomic”
stage of the history, it no doubt meant Deuteronomy; and lastly,
according to modern judgement the book actually discovered was
either the earliest or essential portions of Deuteronomy or possibly a
pre-Deuteronomic prophetic writing demanding the purification of
worship in Jerusalem and urging the abolition of the sacrifices and
feasts at the local shrines.
 Chapter XXXV.
1‒19 (= 1 Esdras i. 1‒22; compare 2 Kings xxiii. 21‒23).
Josiah’s Passover.

Regarding the reference to 1 Esdras i. in the heading above, see

the Introduction § 10, s.v. Greek Versions, where the important fact
is noted that in 1 Esdras we have an old LXX. text, earlier than the
so-called LXX. of Chronicles, and representing a Hebrew text older
than the present Masoretic form. For introduction and notes on the
text of 1 Esdras see the edition by S. A. Cook in Charles’ Apocrypha,
vol. i.

¹And Josiah kept a passover unto the Lord

in Jerusalem: and they killed the passover on
the fourteenth day of the first month.
1. the first month] The legal month was Nisan, or as it was called
in pre-exilic times Abib; compare Exodus xii. Compare also xxx. 2
(with note).

²And he set the priests in their charges, and

encouraged them to the service of the house
of the Lord.
2. in their charges] i.e. at their duties.

encouraged them] As Hezekiah had done; compare xxix. 5‒11,

xxx. 22.
 ³And he said unto the Levites that taught all
Israel, which were holy unto the Lord, Put the
holy ark in the house which Solomon the son
of David king of Israel did build; there shall no
more be a burden upon your shoulders: now
serve the Lord your God, and his people
Israel.
3. that taught all Israel] Compare Nehemiah viii. 7, 9.

Put the holy ark in the house] This rather curious remark seems
to imply that the ark had been removed from the Temple either by
Manasseh or by Josiah during the repairing of the house. The
Levites are bidden to set it in its place without delay, and to devote
themselves to the tasks related in verses 4 ff.

⁴And prepare yourselves after your fathers’

houses by your courses, according to the
writing of David king of Israel, and according
to the writing of Solomon his son.
4. the writing of David] Compare 1 Chronicles xxiii. 27, xxviii. 19‒
21.

⁵And stand in the holy place according to the

divisions of the fathers’ houses of your
brethren the children of the people, and let
there be for each a portion of a fathers’ house ¹
of the Levites.
¹ Or, and according to the distribution of each fathers’ house.
 5. the children of the people] i.e. the laity. The same phrase is
translated in 2 Kings xxiii. 6 “the common people” (without any
invidious meaning).

let there be for each a portion ... of the Levites] Each great
division of the laity was to be served by a small division of the
Levites.

⁶And kill the passover, and sanctify

yourselves, and prepare for your brethren, to
do according to the word of the Lord by the
hand of Moses.
6. prepare for your brethren] Compare verses 12, 13.

⁷And Josiah gave ¹ to the children of the

people, of the flock, lambs and kids, all of
them for the passover offerings, unto all that
were present, to the number of thirty
thousand, and three thousand bullocks: these
were of the king’s substance.
¹ Or, gave for offerings and so in verses 8, 9. See chapter xxx.
24.

7. gave] margin gave for offerings; compare xxx. 24, where it is

said that Hezekiah did the same at his great Passover.

⁸And his princes gave for ¹ a freewill offering

unto the people, to the priests, and to the
Levites. Hilkiah and Zechariah and Jehiel, the
rulers of the house of God, gave unto the
 priests for the passover offerings two
thousand and six hundred small cattle, and
three hundred oxen.
¹ Or, willingly.

8. for a freewill offering] Better, as Authorized Version and

margin, willingly.

Jehiel] 1 Esdras (Ἠσύηλος) suggests a different name, probably

Haziel.

rulers of the house of God] Compare 1 Chronicles ix. 11, note.

⁹Conaniah also, and Shemaiah and Nethanel,

his brethren, and Hashabiah and Jeiel and
Jozabad, the chiefs of the Levites, gave unto
the Levites for the passover offerings five
thousand small cattle, and five hundred oxen.
9. Conaniah ... and Shemaiah] Compare the “Conaniah and
Shimei his brother” of xxxi. 12, and for Jozabad compare the
“Jozabad” of xxxi. 13. Different persons, however, must surely be
meant, or perhaps the names represent families rather than
individuals; nearly sixty years separate the reigns of Hezekiah and
Josiah.

¹⁰So the service was prepared, and the priests

stood in their place, and the Levites by their
courses, according to the king’s
commandment.
 10‒13. The variations in 1 Esdras i. 10‒12 are
misunderstandings of the Hebrew; see Cook, Apocrypha.

¹¹And they killed the passover, and the priests

sprinkled the blood, which they received of
their hand, ¹²and the Levites flayed them. And
they removed the burnt offerings, that they
might give them according to the divisions of
the fathers’ houses of the children of the
people, to offer unto the Lord, as it is written
in the book of Moses. And so did they with the
oxen.
11. sprinkled] Compare xxix. 22, note.

the Levites flayed] Compare xxix. 34.

¹³And they roasted the passover with fire

according to the ordinance: and the holy
offerings sod they in pots, and in caldrons,
and in pans, and carried them quickly to all the
children of the people.
13. the ordinance] Exodus xii. 9.

and the holy offerings] The bullocks mentioned in verses 7, 8, 9.

Possibly these were slain not on the Passover day itself, but on the
days which immediately followed. The practice of later times,
however, seems to have admitted the sacrifice of oxen as a thank
offering along with the Passover lambs (see Mishnah, Pesachim, vi.
3, 4); and it is possible that in the Chronicler’s time oxen were thus
killed and eaten on the Passover day, although they were, as this
verse indicates, prepared differently from the Passover lambs.
 ¹⁴And afterward they prepared for themselves,
and for the priests; because the priests the
sons of Aaron were busied in offering the
burnt offerings and the fat until night: therefore
the Levites prepared for themselves, and for
the priests the sons of Aaron.
14. the fat] Compare vii. 7, note; xxix. 35.

¹⁵And the singers the sons of Asaph were in

their place, according to the commandment of
David, and Asaph, and Heman, and Jeduthun
the king’s seer; and the porters were at every
gate: they needed not to depart from their
service, for their brethren the Levites prepared
for them.
15. the singers] Compare 1 Chronicles xxv. 1 ff.

Heman] But 1 Esdras has Zacharias, a reading which finds some

support in 1 Chronicles xv. 18, xvi. 5.

¹⁶So all the service of the Lord was prepared

the same day, to keep the passover, and to
offer burnt offerings upon the altar of the
Lord, according to the commandment of king
Josiah. ¹⁷And the children of Israel that were
present kept the passover at that time, and the
feast of unleavened bread seven days.
 16. the same day] Literally “on that day,” i.e. the fourteenth of
Nisan.

¹⁸And there was no passover like to that kept

in Israel from the days of Samuel the prophet;
neither did any of the kings of Israel keep such
a passover as Josiah kept, and the priests,
and the Levites, and all Judah and Israel that
were present, and the inhabitants of
Jerusalem.
18. there was no passover like to that kept in Israel from the days
of Samuel] The statement is simply a reproduction of 2 Kings xxiii.
22, where we read “there was not kept such a passover from the
days of the judges that judged Israel ... but in the eighteenth year of
king Josiah was this passover kept to the Lord in Jerusalem.”
Actually the novelty of Josiah’s festival was (i) that it was kept in
Jerusalem, whereas previously the Passover had been a household
feast observed at any “high-place” throughout the country, and
(ii) that it thus marked the inauguration of the system of only one
legitimate sanctuary—Jerusalem—which was codified in
Deuteronomy. The writer in Kings may have clearly understood that
the point lay in the words “in Jerusalem.” To the Chronicler, the
statement meant merely an assertion that this feast was the
grandest Passover since the days of the judges (he prefers to write
since Samuel, reckoning him the last of the judges).

A similar but not identical remark regarding Hezekiah’s Passover

is made in xxx. 26—“since the time of Solomon there was not the
like in Jerusalem.” In some points Hezekiah’s feast as described in
xxx. 1 ff. may be said to have surpassed Josiah’s, but it is most
unnecessary and indeed pedantic so to magnify this fact as to insist
that the sweeping assertion of the present verse about Josiah’s
Passover cannot be from the same source as xxx. 1‒26. Both
passages may well be from the Chronicler (so Curtis, p. 471); in xxx.
1 ff. he was writing a free description of Hezekiah’s feast, and the
verse (xxx. 26) quoted above was written by him to impress us duly
with its magnificence; in the present verse he was naturally
reproducing his source in Kings, and it is most unlikely that he would
notice any slight inconsistency with xxx. 26, or that, if he did, he
would have been troubled thereby.

from the days of Samuel] In 2 Kings xxiii. 22 “from the days of the
judges.”

¹⁹In the eighteenth year of the reign of Josiah

was this passover kept.
19. In the eighteenth year] Comparison of the later Greek version
(the so-called LXX.) of this verse with the earlier Greek version (the
old LXX.) preserved in 1 Esdras reveals that this passage is one of
great interest for the history of the text. After verse 19 “In the
eighteenth year of the reign of Josiah was this passover kept,” 1
Esdras i. 23, 24 has a remarkable addition as follows: “And the
works of Josias were upright before his Lord with a heart full of
godliness. Moreover the things that came to pass in his days [or ‘the
things concerning him’] have been written in times past concerning
... those that sinned and did wickedly against the Lord above every
people and kingdom, and how they grieved him exceedingly, so that
the words of the Lord were confirmed against Israel.” Then follows
verse 25 (compare Hebrew verse 20) “Now after all these acts of
Josias it came to pass that Pharaoh, king of Egypt,” etc. Probably
some words have been lost at the point where the dots are placed.
As it stands, the passage seems to associate the reign of the godly
Josiah with wicked and irreligious doings. The inference to be drawn
is that this passage was originally part of the Hebrew text (from
which the old LXX. was translated), but was subsequently excised
on account of its apparent aspersion on the character of Josiah. The
gap thus created was filled in some Hebrew MSS. by the insertion of
2 Kings xxiii. 24‒27, and from such a Hebrew text the later Greek
version (the present LXX.) was made. In other Hebrew MSS.,
however, the gap was left unfilled, and from one of these was
derived the Hebrew text which has reached us (see Torrey, Ezra
Studies, pp. 87‒89). It is only by the use of the Greek versions that
we are now able to perceive that an omission has been made.

20‒24 (= 1 Esdras i. 25‒31; compare 2 Kings xxiii. 29, 30a).

The Death of Josiah.

The account of Josiah’s death is very much fuller in Chronicles

than in Kings. The features which are peculiar to the Chronicler are,
(1) Neco’s message to dissuade Josiah from war, (2) Josiah’s
disguising himself and coming to fight in the valley of Megiddo,
(3) the wounding of Josiah by archers, (4) the transfer of the
wounded king from a war chariot to another chariot. Thus all the
details which represent the meeting at Megiddo as a battle are
peculiar to Chronicles.

The account given in Kings is simply:—“King Josiah went to meet

him (Neco), and he put him to death at Megiddo when he saw him.
And his servants carried him in a chariot dead from Megiddo, and
brought him to Jerusalem.” The Hebrew expression for “went to
meet” in this passage is the same as in 1 Kings xviii. 16; 2 Kings xvi.
10; it does not suggest a hostile meeting, though it can be used in a
suitable context to describe one. The phrase “when he saw him”
suggests an interview rather than a battle. Thus we have two
versions of Josiah’s death: according to Chronicles he was mortally
wounded in battle, according to Kings he sought an interview with
Neco and was assassinated by him at the town of Megiddo.

These differences may be due to two distinct traditions, but it

seems more probable that the Chronicler’s account is an intentional
adaptation of the Kings narrative to suit the main principles of his
work. We can easily realise that the bald fact of Josiah’s death at the
hands of Neco presented a distressing moral perplexity to the
Chronicler’s mind. Why, when Josiah had been so diligent in the
service of his God, did Jehovah abandon him to death in this
fashion? The stress of the problem is reflected in the rather pathetic
phrase of verse 20, “After all this ... came Neco.” The same words
are used of Hezekiah (xxxii. 1), “After these things and this
faithfulness, Sennacherib came ...,” but in his case the sore trial of
faith proved to be for the greater glory of the God of Israel. Here the
plea of a successful issue to the trouble was not available, and no
doubt the story of Josiah’s end was too famous to be passed over in
silence. It would seem as if the Chronicler therefore adapted the
narrative so as to make it appear that Josiah made an attack on
Neco in defiance of a Divine warning (verse 21), and thus deserved
his fate. The somewhat similar tale of Ahab’s death (xviii. 28‒34 = 1
Kings xxii. 29‒37) was in the Chronicler’s mind, and he appears to
have drawn upon it for certain details introduced into his version of
Josiah’s end (see verses 22, 23).

²⁰After all this, when Josiah had prepared

the temple, Neco king of Egypt went up to
fight against Carchemish by Euphrates: and
Josiah went out against him.
20. Neco] This was Neco II who reigned 610‒594 b.c. (Flinders
Petrie, History of Egypt, iii. 335). According to Herodotus (ii. 159) he
conquered the “Syrians” at “Magdolus,” and then captured Cadytis
(Kadesh on the Orontes, or Gaza?), an important city of Syria.
Herodotus no doubt refers to the same great campaign of Neco
which is recorded in Kings and Chronicles, though it is not at all likely
that the victory over the Syrians at Magdolus is to be identified with
the encounter of Neco and Josiah at Megiddo. The account of
Herodotus is obscure, ambiguous, and defective, but a comparison
of 2 Kings with an inscription of Nabu-na’id king of Babylon (555‒538
b.c.) sets Neco’s action in a clearer light. The campaign (which took
place about 608 b.c.) was directed “against the king of Assyria” (2
Kings xxiii. 29), i.e. against the last king Sin-šariškun (Saracos) who
was at war with Nabopolassar (father of Nebuchadrezzar), king of
Babylon. Nabopolassar, hard pressed, called in to his help the
Umman-manda (Scythians), who destroyed Nineveh circa 607 b.c.;
compare Messerschmidt, Die Inschrift der Stele Nabu-na’id’s (pp. 5‒
13). Neco advanced to the Euphrates to secure some of the spoils of
the Assyrian overthrow, but the crushing victory of Nebuchadrezzar
over Neco at Carchemish (circa 605 b.c.) finally excluded Egypt from
any share.

against Carchemish] compare Jeremiah xlvi. 2. It was a city

situated near the junction of the Habor and Euphrates. In 2 Kings,
“against the king of Assyria.”

²¹But he sent ambassadors to him, saying,

What have I to do with thee, thou king of
Judah? I come not against thee this day, but
against the house wherewith I have war; and
God hath commanded me to make haste ¹:
forbear thee from meddling with God, who is
with me, that he destroy thee not.
¹ Or, hath given command to speed me.

21. against the house wherewith I have war] In 1 Esdras i. 27

there is a different reading, “my war is upon Euphrates.”

²²Nevertheless Josiah would not turn his face

from him, but disguised himself, that he might
fight with him, and hearkened not unto the
words of Neco, from the mouth of God, and
came to fight in the valley of Megiddo.
22. disguised himself] Like Ahab at Ramoth-gilead (xviii. 29), to
reduce the risk. The LXX. reads ἐκραταιώθη, “was strengthened.”
The Hebrew text is probably correct (see Torrey, Ezra Studies, p.
221).

the valley of Megiddo] Compare Judges v. 19; Zechariah xii. 11.

In 1 Esdras i. 29, “the plain of Megiddo.” The whole (or perhaps only