EBOOK - Corrosion Engineering (Volkan Cicek)
Corrosion is, in essence, a chemical process; hence it is crucial to understand the dynamics from a chemical perspective before proceeding with analyses, designs and solutions from an engineering aspect. The opposite is also true in the sense that scientists should take into consideration the contemporary aspects of the issue as it relates to the daily life before proceeding with specifically designed theoretical solutions.
Thus, this book is advised to both theoreticians and practitioners of corrosion alike.
Corrosion is associated primarily with major engineering sciences such as chemical engineering, civil engineering, petroleum engineering as well as with sub-disciplines of major fundamental sciences such as physical, inorganic, and analytical chemistry, surface chemistry and surface physics, electrochemistry, solution chemistry, solid state chemistry and solid state physics, crystalline and amorphous structures, and microbiology.
Hence, a reference book that summarizes the process of corrosion with its contemporary aspects with respect to both scientifi c and engineering aspects was needed. In addition to be used as a reference book, this book could also be used as a textbook most conveniently for a single semester technical elective course; while the period of the course could be adjusted to fit into a long or a short summer term as well as a complete year depending on the nature of the course. In the case that this book is used as a textbook for a full year course, using supplementary resources may be beneficial especially in the case of engineering sciences.
Preface xv
1 Corrosion of Materials 1
1.1 Deterioration or Corrosion of Ceramic Materials 2
1.2 Degradation or Deterioration of Polymers 3
1.3 Corrosion or Deterioration of Metals 4
1.3.1 Iron, Steel and Stainless Steels 4
1.3.2 Aluminum and Its Alloys 9
1.3.3 Magnesium and Its Alloys 14
1.3.4 Copper and Its Alloys 14
1.3.5 Nickel and Its Alloys 15
1.3.6 Titanium and Its Alloys 16
1.3.7 Lead and Its Alloys 16
1.3.8 Composite Alloys 16
2 Cost of Corrosion 21
2.1 Corrosion Preventative Measures 22
2.2 Lost Production Due to Plants Going out of Service or Shutdowns 22
2.3 Product Loss Due to Leakages 22
2.4 Contamination of the Product 23
2.5 Maintenance Costs 23
2.6 Overprotective Measures 23
3 Factors Influencing Corrosion 25
3.1 Nature of the Metal 27
3.1.1 Position in Galvanic Series 27
3.1.2 Relative Areas of the Anode and Cathode 27
3.1.3 Purity of Metal 28
3.1.4 Physical State of the Metal 28
3.1.5 Passivity or Passivation 28
3.1.6 Nature of the Corrosion Product 28
3.1.7 Nature of the Oxide Film 29
3.2 Nature of the Corroding Environment 29
3.2.1 Effect of Temperature 29
3.2.2 Dissolved Oxygen Concentration and Formation of Oxygen Concentration Cells 29
3.2.3 Nature of the Electrolyte 30
3.2.4 Presence of Aggressive Ions 30
3.2.5 Flow Rate 32
3.2.6 Humidity 32
3.2.7 Effect of pH 32
3.2.8 Presence of Impurities in the Atmosphere 32
4 Corrosion Mechanisms 35
4.1 Direct Chemical Attack or Chemical or Dry Corrosion 35
4.1.1 Oxidation Corrosion 36
4.1.2 Corrosion by Other Gases 38
4.1.3 Liquid Metal Corrosion 38
4.2 Electrochemical or Aqueous or Wet Corrosion 38
4.2.1 Electroplating 39
4.2.2 Liberation of Hydrogen 39
4.2.3 Oxygen Absorption 39
4.3 Differences between Chemical and Electrochemical Corrosion 41
5 Types of Corrosion 43
5.1 Uniform Corrosion 43
5.1.1 Atmospheric Corrosion 45
5.1.2 Corrosion in Water 49
5.1.3 Underground or Soil Corrosion 52
5.1.4 High Temperature Corrosion 55
5.2 Non-Uniform Corrosion 56
5.2.1 Galvanic Corrosion 56
5.2.2 Crevice Corrosion 58
5.2.3 Pitting Corrosion 60
5.2.4 Selective Leaching or Selective Corrosion 63
5.2.5 Filiform Corrosion 63
5.2.6 Erosion Corrosion 64
5.2.7 Cavitation Corrosion 66
5.2.8 Abrasion Corrosion 66
5.2.9 Stress Corrosion 67
5.2.10 Intergranular Corrosion 70
5.2.11 Caustic Embrittlement 72
5.2.12 Hydrogen Embrittlement 73
5.2.13 Corrosion Fatigue 75
5.2.14 Fretting Corrosion 77
5.2.15 Stray-current and Interference Corrosion 78
5.2.16 Waterline Corrosion 78
5.2.17 Microbial or Biocorrosion 79
6 Th e Thermodynamics of Corrosion 83
6.1 Gibbs Free Energy (ΔG) 84
6.2 Passivity 85
6.3 Pourbaix Diagrams 87
6.3.1 Immunity Region 88
6.3.2 Corrosion Regions 89
6.3.3 Passivity Region 89
6.4 Corrosion Equilibrium and Adsorptions 89
6.5 Concentration Corrosion Cells 91
6.6 Polarization 93
6.6.1 Activation Polarization 95
6.6.2 Concentration Polarization 95
6.6.3 Ohmic Polarization 96
6.7 Polarization Curves 96
7 Corrosion Prevention and Protection 101
7.1 Proper Design 103
7.2 Choice of Material 105
7.2.1 Naturally Occuring Protective Metal Oxide Films 106
7.2.2 Purity of the Chemicals in the Environment 107
7.2.3 Electrolyte Concentrations 107
7.2.4 Nature of the Electrolyte 107
7.2.5 Effect of Corrosion Products 107
7.2.6 Temperature Variations 107
7.2.7 Presence of Oxygen 108
7.2.8 Oxygen Concentration Cells 108
7.2.9 Interference Effects 108
7.3 Protective Coatings 109
7.3.1 Protective Oxide Films and Passivation 109
7.3.2 Coatings with Metals, Alloys or Materials that are Conductors 111
7.3.3 Coating with Inorganic Materials that are Insulators 114
7.3.4 Coating with Organic Materials that are Insulators 115
7.3.5 Sol-Gels (Ormosils) 117
7.4 Changing the Environmental Factors that Accelerate Corrosion 124
7.4.1 Reducing the Corrosivity of the Solution 125
7.4.2 Inhibitors 126
7.4.3 Types of Corrosion Inhibitors 132
7.4.4 Chromates 133
7.4.5 Oxyanions Analogous to Chromate 142
7.4.6 Eliminating Galvanic Action 147
7.5 Changing the Electrochemical Characteristic of the Metal Surface 147
7.5.1 Anodic Protection 148
7.5.2 Cathodic Protection 149
8 Corrosion and Corrosion Prevention of Concrete Structures 171
8.1 Concrete’s Chemical Composition 172
8.2 Corrosion Reactions of Concrete 173
8.3 Factors Affecting Corrosion Rate in Reinforced
Concrete Structures 174
8.3.1 Effect of Concrete Composition 174
8.3.2 Effect of Oxygen 175
8.3.3 Effect of Humidity 176
8.3.4 Effect of Temperature 177
8.3.5 Effect of pH 177
8.3.6 Effect of Chlorides 179
8.3.7 Effect of Magnesium Ions 182
8.4 Corrosion Measurements in Reinforced Concrete Structures 183
8.4.1 Observational Methods 183
8.4.2 Weight Loss Measurements 183
8.4.3 Potential Diagrams 184
8.4.4 Polarization Curves 185
8.5 Corrosion Prevention of Reinforced Concrete 186
8.5.1 Via Coatings 187
8.5.2 Via Inhibitors 187
8.5.3 Via Cathodic Protection 187
9 Corrosion and Corrosion Prevention of Metallic Structures in Seawater 191
9.1 Factors Affecting Corrosion Rate of Metallic Structures in Seawater 192
9.1.1 Effect of Resistivity on Corrosion in Seawater 192
9.1.2 Effect of pH on Corrosion in Seawater 192
9.1.3 Effect of Temperature on Corrosion in Seawater 193
9.1.4 Effect of Dissolved Oxygen Concentration 193
9.1.5 Effect of Fluid Rate 195
9.2 Cathodic Protection of Metallic Structures in the Sea 195
9.2.1 Cathodic Protection of Ships 195
9.2.2 Cathodic Protection of Pier Poles with Galvanic Anodes 197
10 Corrosion and Corrosion Prevention in Petroleum Industry 199
10.1 Chemicals that Cause Corrosion in Petroleum Industry 201
10.1.1 Hydrochloric Acid (HCl) and Chlorides 201
10.1.2 Hydrogen (H2) Gas 202
10.1.3 Hydrogen Sulfide (H2S) and Other Sulfur Compounds 203
10.1.4 Sulfuric Acid (H2SO4) 204
10.1.5 Hydrogen Fluoride (HF) 205
10.1.6 Carbon Dioxide (CO2) 205
10.1.7 Dissolved Oxygen (O2) and Water (H2O) 205
10.1.8 Organic Acids 208
10.1.9 Nitrogen (N2) Compounds and Ammonia (NH3) 208
10.1.10 Phenols 209
10.1.11 Phosphoric Acid (H3PO4) 209
10.1.12 Caustic Soda (NaOH) 209
10.1.13 Mercury (Hg) 210
10.1.14 Aluminum Chloride (AlCl3) 210
10.1.15 Sulfate Reducing Bacteria (SRB) 210
10.2 Petroleum or Crude Oil Pipeline Systems 211
10.2.1 Cathodic Protection of Pipeline Systems 213
10.2.2 Cathodic Protection of Airport Fuel Distribution Lines 213
10.3 Crude Oil or Petroleum Storage Tanks 214
10.3.1 Cathodic Protection of Inner Surfaces of Crude Oil Storage Tanks 215
10.3.2 Corrosion Prevention 215
11 Corrosion and Corrosion Prevention in Water Transportation and Storage Industry 217
11.1 Water Pipeline Systems 217
11.1.1 Water Pipelines Made of Iron and Its Alloys 218
11.1.2 Galvanized Water Pipelines 219
11.1.3 Water Pipelines Made of Copper 220
11.1.4 Water Pipelines Made of Brass 220
11.1.5 Cathodic Protection of Water Pipelines 221
11.2 Cooling Water Systems 221
11.3 Potable Water Tanks 222
11.4 Boilers 222
11.4.1 Corrosion in Boilers 223
11.4.2 Corrosion Prevention in Boilers 226
11.4.3 Degassing 226
11.4.4 Chemical Conditioning 226
11.5 Geothermal Systems 229
11.5.1 Corrosion in Geothermal Systems 229
11.5.2 Corrosion Prevention in Geothermal Systems 229
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Corrosion is, in essence, a chemical process; hence it is crucial to understand the dynamics from a chemical perspective before proceeding with analyses, designs and solutions from an engineering aspect. The opposite is also true in the sense that scientists should take into consideration the contemporary aspects of the issue as it relates to the daily life before proceeding with specifically designed theoretical solutions.
Thus, this book is advised to both theoreticians and practitioners of corrosion alike.
Corrosion is associated primarily with major engineering sciences such as chemical engineering, civil engineering, petroleum engineering as well as with sub-disciplines of major fundamental sciences such as physical, inorganic, and analytical chemistry, surface chemistry and surface physics, electrochemistry, solution chemistry, solid state chemistry and solid state physics, crystalline and amorphous structures, and microbiology.
Hence, a reference book that summarizes the process of corrosion with its contemporary aspects with respect to both scientifi c and engineering aspects was needed. In addition to be used as a reference book, this book could also be used as a textbook most conveniently for a single semester technical elective course; while the period of the course could be adjusted to fit into a long or a short summer term as well as a complete year depending on the nature of the course. In the case that this book is used as a textbook for a full year course, using supplementary resources may be beneficial especially in the case of engineering sciences.
Preface xv
1 Corrosion of Materials 1
1.1 Deterioration or Corrosion of Ceramic Materials 2
1.2 Degradation or Deterioration of Polymers 3
1.3 Corrosion or Deterioration of Metals 4
1.3.1 Iron, Steel and Stainless Steels 4
1.3.2 Aluminum and Its Alloys 9
1.3.3 Magnesium and Its Alloys 14
1.3.4 Copper and Its Alloys 14
1.3.5 Nickel and Its Alloys 15
1.3.6 Titanium and Its Alloys 16
1.3.7 Lead and Its Alloys 16
1.3.8 Composite Alloys 16
2 Cost of Corrosion 21
2.1 Corrosion Preventative Measures 22
2.2 Lost Production Due to Plants Going out of Service or Shutdowns 22
2.3 Product Loss Due to Leakages 22
2.4 Contamination of the Product 23
2.5 Maintenance Costs 23
2.6 Overprotective Measures 23
3 Factors Influencing Corrosion 25
3.1 Nature of the Metal 27
3.1.1 Position in Galvanic Series 27
3.1.2 Relative Areas of the Anode and Cathode 27
3.1.3 Purity of Metal 28
3.1.4 Physical State of the Metal 28
3.1.5 Passivity or Passivation 28
3.1.6 Nature of the Corrosion Product 28
3.1.7 Nature of the Oxide Film 29
3.2 Nature of the Corroding Environment 29
3.2.1 Effect of Temperature 29
3.2.2 Dissolved Oxygen Concentration and Formation of Oxygen Concentration Cells 29
3.2.3 Nature of the Electrolyte 30
3.2.4 Presence of Aggressive Ions 30
3.2.5 Flow Rate 32
3.2.6 Humidity 32
3.2.7 Effect of pH 32
3.2.8 Presence of Impurities in the Atmosphere 32
4 Corrosion Mechanisms 35
4.1 Direct Chemical Attack or Chemical or Dry Corrosion 35
4.1.1 Oxidation Corrosion 36
4.1.2 Corrosion by Other Gases 38
4.1.3 Liquid Metal Corrosion 38
4.2 Electrochemical or Aqueous or Wet Corrosion 38
4.2.1 Electroplating 39
4.2.2 Liberation of Hydrogen 39
4.2.3 Oxygen Absorption 39
4.3 Differences between Chemical and Electrochemical Corrosion 41
5 Types of Corrosion 43
5.1 Uniform Corrosion 43
5.1.1 Atmospheric Corrosion 45
5.1.2 Corrosion in Water 49
5.1.3 Underground or Soil Corrosion 52
5.1.4 High Temperature Corrosion 55
5.2 Non-Uniform Corrosion 56
5.2.1 Galvanic Corrosion 56
5.2.2 Crevice Corrosion 58
5.2.3 Pitting Corrosion 60
5.2.4 Selective Leaching or Selective Corrosion 63
5.2.5 Filiform Corrosion 63
5.2.6 Erosion Corrosion 64
5.2.7 Cavitation Corrosion 66
5.2.8 Abrasion Corrosion 66
5.2.9 Stress Corrosion 67
5.2.10 Intergranular Corrosion 70
5.2.11 Caustic Embrittlement 72
5.2.12 Hydrogen Embrittlement 73
5.2.13 Corrosion Fatigue 75
5.2.14 Fretting Corrosion 77
5.2.15 Stray-current and Interference Corrosion 78
5.2.16 Waterline Corrosion 78
5.2.17 Microbial or Biocorrosion 79
6 Th e Thermodynamics of Corrosion 83
6.1 Gibbs Free Energy (ΔG) 84
6.2 Passivity 85
6.3 Pourbaix Diagrams 87
6.3.1 Immunity Region 88
6.3.2 Corrosion Regions 89
6.3.3 Passivity Region 89
6.4 Corrosion Equilibrium and Adsorptions 89
6.5 Concentration Corrosion Cells 91
6.6 Polarization 93
6.6.1 Activation Polarization 95
6.6.2 Concentration Polarization 95
6.6.3 Ohmic Polarization 96
6.7 Polarization Curves 96
7 Corrosion Prevention and Protection 101
7.1 Proper Design 103
7.2 Choice of Material 105
7.2.1 Naturally Occuring Protective Metal Oxide Films 106
7.2.2 Purity of the Chemicals in the Environment 107
7.2.3 Electrolyte Concentrations 107
7.2.4 Nature of the Electrolyte 107
7.2.5 Effect of Corrosion Products 107
7.2.6 Temperature Variations 107
7.2.7 Presence of Oxygen 108
7.2.8 Oxygen Concentration Cells 108
7.2.9 Interference Effects 108
7.3 Protective Coatings 109
7.3.1 Protective Oxide Films and Passivation 109
7.3.2 Coatings with Metals, Alloys or Materials that are Conductors 111
7.3.3 Coating with Inorganic Materials that are Insulators 114
7.3.4 Coating with Organic Materials that are Insulators 115
7.3.5 Sol-Gels (Ormosils) 117
7.4 Changing the Environmental Factors that Accelerate Corrosion 124
7.4.1 Reducing the Corrosivity of the Solution 125
7.4.2 Inhibitors 126
7.4.3 Types of Corrosion Inhibitors 132
7.4.4 Chromates 133
7.4.5 Oxyanions Analogous to Chromate 142
7.4.6 Eliminating Galvanic Action 147
7.5 Changing the Electrochemical Characteristic of the Metal Surface 147
7.5.1 Anodic Protection 148
7.5.2 Cathodic Protection 149
8 Corrosion and Corrosion Prevention of Concrete Structures 171
8.1 Concrete’s Chemical Composition 172
8.2 Corrosion Reactions of Concrete 173
8.3 Factors Affecting Corrosion Rate in Reinforced
Concrete Structures 174
8.3.1 Effect of Concrete Composition 174
8.3.2 Effect of Oxygen 175
8.3.3 Effect of Humidity 176
8.3.4 Effect of Temperature 177
8.3.5 Effect of pH 177
8.3.6 Effect of Chlorides 179
8.3.7 Effect of Magnesium Ions 182
8.4 Corrosion Measurements in Reinforced Concrete Structures 183
8.4.1 Observational Methods 183
8.4.2 Weight Loss Measurements 183
8.4.3 Potential Diagrams 184
8.4.4 Polarization Curves 185
8.5 Corrosion Prevention of Reinforced Concrete 186
8.5.1 Via Coatings 187
8.5.2 Via Inhibitors 187
8.5.3 Via Cathodic Protection 187
9 Corrosion and Corrosion Prevention of Metallic Structures in Seawater 191
9.1 Factors Affecting Corrosion Rate of Metallic Structures in Seawater 192
9.1.1 Effect of Resistivity on Corrosion in Seawater 192
9.1.2 Effect of pH on Corrosion in Seawater 192
9.1.3 Effect of Temperature on Corrosion in Seawater 193
9.1.4 Effect of Dissolved Oxygen Concentration 193
9.1.5 Effect of Fluid Rate 195
9.2 Cathodic Protection of Metallic Structures in the Sea 195
9.2.1 Cathodic Protection of Ships 195
9.2.2 Cathodic Protection of Pier Poles with Galvanic Anodes 197
10 Corrosion and Corrosion Prevention in Petroleum Industry 199
10.1 Chemicals that Cause Corrosion in Petroleum Industry 201
10.1.1 Hydrochloric Acid (HCl) and Chlorides 201
10.1.2 Hydrogen (H2) Gas 202
10.1.3 Hydrogen Sulfide (H2S) and Other Sulfur Compounds 203
10.1.4 Sulfuric Acid (H2SO4) 204
10.1.5 Hydrogen Fluoride (HF) 205
10.1.6 Carbon Dioxide (CO2) 205
10.1.7 Dissolved Oxygen (O2) and Water (H2O) 205
10.1.8 Organic Acids 208
10.1.9 Nitrogen (N2) Compounds and Ammonia (NH3) 208
10.1.10 Phenols 209
10.1.11 Phosphoric Acid (H3PO4) 209
10.1.12 Caustic Soda (NaOH) 209
10.1.13 Mercury (Hg) 210
10.1.14 Aluminum Chloride (AlCl3) 210
10.1.15 Sulfate Reducing Bacteria (SRB) 210
10.2 Petroleum or Crude Oil Pipeline Systems 211
10.2.1 Cathodic Protection of Pipeline Systems 213
10.2.2 Cathodic Protection of Airport Fuel Distribution Lines 213
10.3 Crude Oil or Petroleum Storage Tanks 214
10.3.1 Cathodic Protection of Inner Surfaces of Crude Oil Storage Tanks 215
10.3.2 Corrosion Prevention 215
11 Corrosion and Corrosion Prevention in Water Transportation and Storage Industry 217
11.1 Water Pipeline Systems 217
11.1.1 Water Pipelines Made of Iron and Its Alloys 218
11.1.2 Galvanized Water Pipelines 219
11.1.3 Water Pipelines Made of Copper 220
11.1.4 Water Pipelines Made of Brass 220
11.1.5 Cathodic Protection of Water Pipelines 221
11.2 Cooling Water Systems 221
11.3 Potable Water Tanks 222
11.4 Boilers 222
11.4.1 Corrosion in Boilers 223
11.4.2 Corrosion Prevention in Boilers 226
11.4.3 Degassing 226
11.4.4 Chemical Conditioning 226
11.5 Geothermal Systems 229
11.5.1 Corrosion in Geothermal Systems 229
11.5.2 Corrosion Prevention in Geothermal Systems 229
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