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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