Atmospheric Corrosion

Christofer Leygraf is Professor Emeritus at KTH Royal Institute of Technology, Division of Surface and Corrosion Science, Stockholm, Sweden. Inger Odnevall Wallinder is Professor at KTH Royal Institute of Technology, Division of Surface and Corrosion Science, Stockholm, Sweden. Johan Tidblad is Manager for the Section Corrosion Protection and Surface Technology at Swerea KIMAB, Stockholm, Sweden. Thomas Graedel is Professor Emeritus at Yale School of Forestry and Environmental Studies, New Haven, Connecticut, USA.

Preface xv

1 The Many Faces of Atmospheric Corrosion 1

1.1 Dr. Vernon’s Legacy 1

1.2 Concepts and Consequences 2

1.3 The Evolution of a Field 3

1.4 Controlled Laboratory Environments 4

1.5 Uncontrolled Field Environments 5

1.6 New Approaches to Atmospheric Corrosion Studies 6

1.7 An Overview of this Book 6

2 A Conceptual Picture of Atmospheric Corrosion 7

2.1 Introduction 7

2.2 Initial Stages of Atmospheric Corrosion 7

2.3 Intermediate Stages of Atmospheric Corrosion 11

2.4 Final Stages of Atmospheric Corrosion 17

Further Reading 20

3 A Multiregime Perspective on Atmospheric Corrosion Chemistry 22

3.1 Introduction to Moist‐Layer Chemistry 22

3.2 The Gaseous Regime 24

3.3 The Interface Regime 25

3.4 The Liquid Regime 27

3.5 The Deposition Regime 28

3.6 The Electrodic Regime 30

3.7 The Solid Regime 31

3.8 The Multiregime Perspective 32

Further Reading 32

4 Atmospheric Gases and their Involvement in Corrosion 34

4.1 Chemical Species of Interest 34

4.2 Atmospheric Corrosive Gases 35

4.3 Historic Trends in Atmospheric Corrosive Gas Concentrations 40

4.4 Predicted Future Emissions of Corrosive Species 43

Further Reading 45

5 Atmospheric Particles and their Involvement in Corrosion 46

5.1 Introduction 46

5.2 Chemical Species of Interest 49

5.3 Sources of Atmospheric Aerosol Particles 50

5.4 Aerosol Particle Physics and Chemistry 51

5.5 Implications of Aerosol Particles for Atmospheric Corrosion 55

Further Reading 57

6 Corrosion in Laboratory Exposures 59

6.1 The Need for Well‐Defined Laboratory Experiments 59

6.2 Considerations for Specific Metals 59

6.3 Design Considerations 60

6.4 Examples of Important Laboratory Exposures 65

6.5 Can Corrosion Processes in the Field be Reasonably Simulated by Laboratory Experiments? 67

6.6 Computational Model Studies of SO2 ‐Induced Atmospheric Corrosion of Copper 70

6.7 Summary 76

Further Reading 77

7 Corrosion in Indoor Exposures 79

7.1 General Characteristics of Indoor Environments 79

7.2 The Interplay Between Pollutants and Corrosion Rates 85

7.3 Corrosion Rates 88

7.4 Indoor Corrosion Products 93

7.5 Indoor Environmental Classification 94

7.6 An Example of Indoor Corrosion: Metal Artifacts 95

7.7 Summary 98

Further Reading 99

8 Corrosion in Outdoor Exposures 100

8.1 The Effect of Exposure Conditions 100

8.2 Design Considerations 101

8.3 Influence of Exposure Parameters 103

8.4 Dose–Response Functions 114

8.5 Summary 118

Further Reading 118

9 Advanced Stages of Corrosion 121

9.1 Introduction 121

9.2 Evolution of Corrosion Products on Zinc 122

9.3 Evolution of Corrosion Products on Copper 131

9.4 Evolution of Corrosion Products on Carbon Steel 140

9.5 Evolution of Corrosion Products on Aluminum 144

9.6 Summary 146

Further Reading 148

10 Environmental Dispersion of Metals From Corroded Outdoor Constructions 151

10.1 Introduction 151

10.2 Metal Dispersion (Runoff): Atmospheric Corrosion 152

10.3 Time‐Dependent Aspects and Importance of Rain and Environmental Conditions 154

10.4 Influence of Construction Geometry on the Metal Runoff and Runoff Rate Predictions 159

10.5 Environmental Fate and Speciation: Importance for Risk Assessment and Management 162

Further Reading 163

11 Applied Atmospheric Corrosion: Electronic Devices 166

11.1 Introduction 166

11.2 Corrosion‐Induced Failures of Contacts and Connectors 168

11.3 Corrosion‐Induced Failures of Integrated Circuits 170

11.4 Accelerated Tests of Electronics 174

11.5 Classification of Environments with Respect to Corrosivity 175

11.6 Methods of Protection 177

Further Reading 180

12 Applied Atmospheric Corrosion: Automotive Corrosion and Corrosion in the Road Environment 181

12.1 Introduction 181

12.2 Typical Corrosion Rates in the Road Environment 182

12.3 Parameters Affecting Corrosion in Road Environments 183

12.4 Corrosion of Vehicles 188

12.5 Accelerated Corrosion Testing for Automotive Applications 190

Further Reading 196

13 Applied Atmospheric Corrosion: Alloys in Architecture 198

13.1 Introduction 198

13.2 Varying Exposure Conditions 199

13.3 Copper‐Based Alloys 200

13.4 Aluminum–Zinc Alloys 208

13.5 Weathering Steel 214

13.6 Stainless Steel 218

Further Reading 221

14 Applied Atmospheric Corrosion: Unesco Cultural Heritage Sites 224

14.1 Introduction 224

14.2 Description of Selected Sites 225

14.3 Estimation of Corrosion Rates 227

14.4 Estimation of Corrosion Costs 229

14.5 Preventing Further Damage Through Air Quality Policy 234

Further Reading 236

15 Scenarios for Atmospheric Corrosion in the Twenty‐First Century 238

15.1 Atmospheric Corrosion in the Recent Millenium 239

15.2 Atmospheric Corrosion in the Twentieth Century and Today 240

15.3 Atmospheric Corrosion in the Twenty‐First Century: Effect of Changes in Pollution 242

15.4 Atmospheric Corrosion in the Twenty‐First Century: Effect of Changes in Climate 246

15.5 Responding to Increasing Rates of Corrosion 246

Further Reading 248

Appendix A Experimental Techniques in Atmospheric Corrosion 249

A.1 Introduction 249

A.2 Techniques for Detecting Mass Change 250

A.3 Techniques for Analyzing Surface Topography 251

A.4 Techniques for Analyzing Surface Composition 253

A.5 Techniques for Identifying Phases in Corrosion Products 255

A.6 Techniques for Corrosion Electrode Potential 256

A.7 Techniques for Monitoring Atmospheric Corrosive Species 258

A.8 Summary 259

Further Reading 260

Appendix B Computer Models of Atmospheric Corrosion 261

B.1 Formulating Computer Models 261

B.2 The Status of Computer Models of Atmospheric Corrosion 262

B.3 An Overview of Chemical Model Formulation 263

B.4 The Transport of Reactants 265

B.5 Physicochemical Processes 266

B.6 Electrochemical Processes 268

Further Reading 270

Appendix C The Atmospheric Corrosion Chemistry of Aluminum 272

C.1 Introduction 272

C.2 Corrosion Layer Formation Rates 272

C.3 The Morphology of Atmospheric Corrosion Layers on Aluminum 273

C.4 Chemical Mechanisms of Corrosion 274

C.5 Summary 280

Appendix D The Atmospheric Corrosion Chemistry of Carbonate Stone 282

D.1 Introduction 282

D.2 Corrosion Layer Formation Rates 282

D.3 Morphology of Atmospheric Corrosion on Carbonate Stone 283

D.4 Chemical Mechanisms of Carbonate Stone Corrosion 284

D.5 Summary 288

Appendix E The Atmospheric Corrosion Chemistry of Copper 290

E.1 Introduction 290

E.2 Corrosion Layer Formation Rates 291

E.3 The Morphology of Natural Patinas on Copper 291

E.4 Chemical Mechanisms of Copper Corrosion 292

E.5 Discussion 300

Appendix F The Atmospheric Corrosion Chemistry of Iron and Low Alloy Steels 302

F.1 Introduction 302

F.2 Formation Rates for Rust Layers 302

F.3 The Morphology of Natural Rust Layers 303

F.4 Chemical Mechanisms of Iron and Steel Corrosion 304

F.5 Stainless Steels in the Atmosphere 313

F.6 Summary 313

Appendix G The Atmospheric Corrosion Chemistry of Lead 316

G.1 Introduction 316

G.2 Environmental Interactions with Lead Surfaces 316

G.3 Physical Characteristics of Lead Corrosion 317

G.4 Chemical Mechanisms of Lead Corrosion 317

G.5 Physical and Chemical Characteristics of Corroding Lead Alloys 324

G.6 Summary 324

Further Reading 326

Appendix H The Atmospheric Corrosion Chemistry of Nickel 327

H.1 Introduction 327

H.2 Corrosion Layer Formation Rates 327

H.3 The Morphology of Atmospheric Corrosion Layers on Nickel 328

H.4 Chemical Mechanisms of Nickel Corrosion 328

H.5 Laboratory and Computational Studies of Nickel’s Atmospheric Corrosion 334

H.6 Conclusions 335

Further Reading 336

Appendix I The Atmospheric Corrosion Chemistry of Silver 337

I.1 Introduction 337

I.2 Environmental Interactions with Silver Surfaces 337

I.3 Chemical Mechanisms of Silver Corrosion 339

I.4 Physical Characteristics of Silver Corrosion 343

I.5 Chemical Transformation Sequences 345

Further Reading 347

Appendix J The Atmospheric Corrosion Chemistry of Zinc 348

J.1 Introduction 348

J.2 Corrosion Layer Formation Rates 348

J.3 The Morphology of Atmospheric Corrosion Layers on Zinc 349

J.4 Chemical Mechanisms of Zinc Corrosion 349

J.5 Transformation Processes 357

J.6 Summary 358

Appendix K Index of Minerals Related to Atmospheric Corrosion 360

Glossary 363

Index 367