LaQue's Handbook of Marine Corrosion

David A. Shifler, Office of Naval Research, Naval Materials Division, U.S. Department of the Navy, USA. Dr Shifler has over 35 years of work experience as a materials and corrosion engineer and has published extensively on corrosion and performance of materials in corrosive environments. He is a Certified Corrosion Specialist with NACE International and a Fellow of the UK Institute of Corrosion, NACE International, ASM International, and the Washington Academy of Sciences.

• List of Contributors xixPreface xxi1 The Nature of Marine Environments 1Bopinder Phull1.1 Introduction 11.2 Seawater Chemistry 21.2.1 Chemical Composition of Seawater 21.2.1.1 Role of Ions 31.2.1.2 Dissolved Gases 51.2.1.3 Scale-Forming Compounds 81.2.1.4 Suspended Matter 91.2.1.5 pH 101.2.1.6 Chlorination 101.3 Physical 111.3.1 Temperature 111.3.2 Electrolytic Resistivity of Seawater 131.3.3 Velocity Effects 141.3.4 Effects of Depth 171.3.5 Splash and Tidal Zones 181.3.6 Bottom Sediments 201.4 Biological Effects 211.4.1 Microorganisms, Biofilms, and Biofouling 211.5 Testing 24References 252 Electrochemistry and Forms of Corrosion 29David A. Shifler2.1 Introduction 292.2 Corrosion Thermodynamics 302.3 Corrosion Kinetics 302.4 Passivity 332.5 Corrosion Mechanistic Modes 342.5.1 Stray Current Corrosion 352.5.2 Galvanic Corrosion 352.5.3 Crevice Corrosion 372.5.4 Pitting 382.5.5 Intergranular Corrosion 382.5.6 Microbiological-Influenced Corrosion 402.5.7 Dealloying 412.5.8 Flow-Influenced Corrosion 422.6 Environmentally Induced Cracking 432.6.1 Stress Corrosion Cracking 432.6.2 Fatigue and Corrosion Fatigue 442.6.3 High-Temperature Corrosion 452.7 Factors Influencing Corrosion 46References 473 Atmospheric Corrosion in Marine Environments 49David G. Enos3.1 Introduction 493.2 Understanding the Environment (Important Factors) 493.2.1 Humidity 513.2.2 Temperature 533.2.3 Solid and Liquid Contaminants (Salt Particulates, Seawater Aerosol, Dust, etc.) 533.2.4 Gaseous Contaminants 553.2.5 Physical Environment 553.3 Basic Electrochemistry of Atmospheric Corrosion 573.4 Corrosion Testing 593.4.1 Accelerated Testing 593.4.2 Long-Term Field Testing 593.5 Modeling 593.6 Summary 60Acknowledgment 60References 604 Localized Corrosion 63David A. Shifler4.1 Introduction 634.2 Pitting 634.2.1 Cast Irons 654.2.2 Carbon Steels 664.2.3 Stainless Steels 664.2.4 Nickel Alloys 694.2.5 Aluminum Alloys 724.2.6 Copper Alloys 734.2.7 Titanium Alloys 774.3 Crevice Corrosion 784.3.1 Cast Irons 814.3.2 Carbon Steels 824.3.3 Stainless Steels 824.3.4 Nickel Alloys 864.3.5 Aluminum Alloys 894.3.6 Copper Alloys 914.3.7 Titanium Alloys 924.4 Intergranular Corrosion 934.4.1 Cast Irons 944.4.2 Carbon Steels 944.4.3 Stainless Steels 954.4.4 Nickel Alloys 974.4.5 Aluminum Alloys 984.4.6 Copper Alloys 1014.4.7 Titanium Alloys 1024.5 Dealloying 1024.5.1 Cast Irons 1034.5.2 Carbon Steels 1044.5.3 Stainless Steels 1044.5.4 Nickel Alloys 1044.5.5 Aluminum Alloys 1044.5.6 Copper Alloys 1054.5.7 Titanium Alloys 108References 108Further Reading 1215 Galvanic Corrosion 123Roger Francis5.1 Introduction 1235.2 Conditions Necessary for Galvanic Corrosion 1245.3 Factors Affecting Galvanic Corrosion 1255.3.1 Electrode Potential 1255.3.2 Potential Variability 1265.3.3 Electrode Efficiency 1275.3.4 Electrolyte 1295.3.5 Area Ratio 1295.3.6 Aeration and Flow Rate 1325.3.7 Metallurgical Condition and Composition 1335.3.8 Stifling Effects 1345.4 Alloy Groups 1355.4.1 Group 1 Alloys 1365.4.2 Group 2 Alloys 1365.4.3 Group 3 Alloys 1385.4.4 Group 4 Alloys 1405.5 Marine Atmospheres 1425.5.1 Factors Affecting Atmospheric Corrosion 1425.5.2 Materials Compatibility 1435.5.3 Atmospheric Variability 1455.5.4 Tropical Atmospheres 1455.6 Methods of Prevention 1475.6.1 Materials 1475.6.2 Insulation and Separation 1475.6.3 Painting/Coatings 1485.6.4 Cathodic Protection (CP) 1495.6.5 Inhibitors 1505.7 Design 150References 1516 The Effects of Turbulent Flow on Corrosion in Seawater 155K. Daniel Efird6.1 Introduction 1556.1.1 Evaluating Flow Effects 1556.2 The Basics of Turbulent Flow and Corrosion 1566.2.1 The Nature of Turbulent Flow 1566.2.2 Disturbed Flow 1596.3 Erosion-Corrosion 1596.3.1 Cavitation Corrosion 1606.4 Flow Effects for Specific Materials 1616.4.1 Carbon and Low Alloy Steels and Cast Irons 1616.4.2 Copper Alloys 1626.4.3 Passive Alloys 1636.5 Flow Effects in Specific Facility Applications 1646.A Wall Shear Stress and Mass Transfer Coefficient Defined 1676.A.1 Wall Shear Stress 1676.A.2 Mass Transfer Coefficient 1686.A.3 Interrelationship of Mass Transfer Coefficient and Wall Shear Stress 1686.B University of Tulsa Erosion Model 169References 1697 Biological Fouling and Corrosion Processes 173Brenda J. Little and Jason S. Lee7.1 Introduction 1737.2 Development of Marine Fouling 1747.2.1 Microfouling 1747.2.2 Macrofouling 1767.3 Influence of Marine Fouling on Corrosion 1777.3.1 Corrosion Mechanisms Related to Generic Properties of Fouling Organisms 1777.3.1.1 Oxygen Concentration Cells 1777.3.1.2 Ennoblement 1787.3.1.3 Galvanic Corrosion 1787.3.2 Reactions Attributed to Specific Groups of Bacteria and Archaea 1797.3.2.1 Sulfate Reduction 1797.3.2.2 Sulfide Reactions with Specific Metals 1797.3.2.3 Acid Production 1817.3.2.4 Microbial Oxidation/Reduction of Iron 1817.4 Diagnosis 1827.5 Control and Prevention 1827.5.1 Coatings 1837.5.2 Biocidal Treatments 1837.5.3 Cathodic Protection 1837.5.4 Deoxygenation 1847.5.5 Flow 1857.6 Commentary 185References 1868 Marine Biofouling 191Simone Dürr, Robert Edyvean, and Eleanor Ramsden-Lister8.1 What Is Biofouling? 1918.2 Development of Biofouling on New Artificial Surfaces 1928.2.1 Macromolecules (Conditioning Film) 1928.2.2 Bacteria 1928.2.3 Diatoms, Protozoans 1958.2.4 Larvae and Spores 1958.3 Established Biofouling Communities 1978.4 The Effect of Biofouling on the Corrosion of Metals in the Marine Environment 1998.5 Past and Present Antifouling Strategies on Metals Used in the Marine Environment 2018.5.1 Tributyltin (TBT) Self-Polishing Copolymer Paints 2018.5.2 Controlled Depletion Polymers (CDPs)/Self-Polishing Containing Biocides and Booster Biocides 2018.5.3 Foul Release Coatings 2028.5.4 Electrochemical Control 2038.5.5 Electrochlorination 2048.5.6 Ultrasonics for Antifouling 2048.5.7 Mechanical Cleaning and Prevention 2058.5.8 Enzymes 2058.5.9 Biomimetics and Bioinspiration 2068.6 Conclusion 206References 2079 Environmentally Enhanced Fatigue 215James Burns9.1 Introduction 2159.2 Precorrosion Effects 2189.3 Loading Environment Effects 2219.4 Crack Initiation 2219.5 Crack Propagation 2239.5.1 Aluminum 2239.5.2 Titanium 2259.5.3 Steel 2269.6 Effect of Corrosion Mitigation Techniques on Fatigue 2309.7 Conclusion 231References 23210 Effects of Stress – Environment Assisted Cracking 239John R. Scully10.1 Introduction 23910.2 High-Strength Steels 24210.2.1 Physical Metallurgy 24210.2.2 General Susceptibility Trends 24310.2.3 Dependence on Applied Potential 24510.3 Stainless Steels 24910.3.1 Physical Metallurgy 24910.3.2 General Susceptibility Trends 25110.3.3 Dependence on Applied Potential 25410.4 Precipitation Hardened Stainless Steels 25410.4.1 Physical and Mechanical Metallurgy of Precipitation Hardened Stainless Steel 25410.4.2 General Susceptibility Trends 25510.4.3 Effect of Applied Potential 26010.5 Titanium Alloys 26110.5.1 Physical Metallurgy 26110.5.2 General Susceptibility Trends 26310.5.3 Effect of Potential 26410.6 High-Strength Aluminum Alloys 26610.6.1 Physical Metallurgy 26610.6.2 General Susceptibility Trends 26810.6.3 Effects of Potential 27110.7 Nickel Base Alloys 27210.7.1 Physical Metallurgy 27210.7.2 General Susceptibility Trends 27310.7.2.1 Effects of Applied Potential 27710.8 Copper, Copper Alloys, and Aluminum Bronze Alloys 27710.8.1 Physical Metallurgy 27710.8.2 General Susceptibility Trends 27810.9 Magnesium Alloys 27910.9.1 Physical Metallurgy 27910.9.2 General Susceptibility Trends and Effects of Potential 279References 28011 Cathodic Delamination 291Thomas Ramotowski11.1 Introduction 29111.2 Mechanisms for Cathodic Delamination 29311.3 Cathodic Delamination Mitigation Strategies 296References 29812 High Temperature Corrosion in Marine Environments 301David A. Shifler12.1 Introduction 30112.1.1 High Temperature Corrosion and Degradation Processes 30112.2 Boilers 30212.3 Diesel Engines 30612.4 Gas Turbine Engines 30912.4.1 High-Temperature Coatings 31712.4.2 Factors Affecting Operational Life 31912.5 Incinerators 31912.6 Fuels 324References 32813 Design for Corrosion Control in Marine Environments 335David A. Shifler13.1 Introduction 33513.2 General Design Approach 33613.3 Corrosion Control Design Choices for Marine Structures 33913.3.1 Materials 33913.3.2 Organic Coatings 33913.3.3 Metallic Coatings 34013.3.4 Cathodic Protection 34113.3.5 Inhibitors 34113.4 Structural Designs that Minimize Corrosion 34213.5 Inspection to Evaluate Conformance to Design, Repair Criteria 34513.6 Ship Design in Marine Environments 34613.6.1 Military Ships and Assets 34613.6.2 Commercial Ship Design 34813.6.3 Cruise Ship Design 34913.7 Offshore Structural Design in Marine Environments 35013.8 Summary 351References 351Further Reading 353Ships 353Offshore Structures 35414 Modeling of Marine Corrosion Processes 355Jason S. Lee, David G. Enos, Roger Francis, Sean Brossia, and David A. Shifler14.1 Introduction 35514.2 Computational Approaches 35514.3 Assumptions in Modeling 35614.4 Galvanic Corrosion 35714.5 Localized Corrosion 35914.5.1 Crevices 36014.5.2 Cracks 36314.5.3 Pitting 36314.5.4 Intergranular Corrosion 36414.6 General Corrosion 36414.7 Atmospheric Corrosion Models 36514.7.1 Holistic Atmospheric Corrosion Model 36514.7.2 GILDES Model 36614.8 Cathodic Protection 36714.9 Recent Modeling Advances 36914.9.1 Future Directions of DFT 37014.10 Limitations and Future Needs 37114.11 Summary 372References 37315 Marine Corrosion Testing 379David A. Shifler and David G. Enos15.1 Introduction 37915.2 Corrosion Test Planning 37915.3 Types of Corrosion Testing 38115.3.1 Laboratory Testing 38115.3.2 Salt Spray/Salt Fog Testing 38315.3.2.1 Types of Salt Spray Environments 38415.3.2.2 Limitations of Salt Spray Testing 38515.3.3 Mixed Flowing Gas (MFG) Exposure Testing 38615.3.4 Immersion Testing 38915.3.5 Electrochemical Testing 39315.3.5.1 Direct Current Electrochemical Methods 39315.3.5.2 Nondestructive Electrochemical Methods 39615.3.6 High Velocity Flow Testing 39715.3.7 Environmental Cracking Test Methods 39815.3.8 High Temperature Testing – Burner-Rigs 40115.3.9 Molten Salt Tests 40115.3.9.1 Thermogravimetric Analysis 40215.3.10 Microbiological Tests 40315.4 Field Evaluation 40515.4.1 In-Service Testing 40815.4.1.1 Simulated Service Testing 41015.4.2 Standards for Seawater Testing 410References 41216 Nonmetallic Materials in Marine Service 421Wayne Tucker16.1 Introduction 42116.2 Selection and Application 42216.2.1 Material Definitions 42216.2.2 Resistance to Environmental Factors 42316.2.3 Mechanical and Physical Properties 42316.3 Wood 42416.3.1 Introduction 42416.3.2 Degrading Factors 42416.4 Plywood and Other Wood Composites 42716.5 Concrete 42816.5.1 Introduction 42816.5.2 Marine Environmental Effects 42916.5.3 Protection of Reinforced Concrete 43016.5.4 Epoxy Coated Rebars (ECR) 43116.5.5 Fiber Reinforced Concrete (FRC) 43216.5.6 Repairs 43216.6 Polymers 43316.6.1 Fiber Reinforced Plastics (FRPs) 43316.6.2 Environmental Effects 43516.6.3 Fatigue of Marine Composites 43616.6.4 Microbial Degradation 43616.6.5 Ceramics and Glass 436References 43717 Electronics and Electrical Equipment in a Marine Environment 441James A. Ellor17.1 Introduction 44117.2 Primary Corrosion Phenomena in a Marine Environment 44217.2.1 Types of Corrosion 44417.2.1.1 Galvanic Corrosion 44417.2.1.2 Electrolytic Corrosion 44517.2.1.3 Electrochemical Migration 44517.3 Protection from the Environment 44617.3.1 Conformal Coatings 44617.3.2 Enclosures 44717.3.3 Hermetic Seals 44817.3.4 Dehumidification 44817.3.5 Corrosion Inhibitors 44917.3.6 Water-Displacing Compounds 44917.4 Corrosion Testing for Electronics in a Marine Environment 44917.5 Conclusions 450References 45118 Structural Alloys in Marine Service 453David A. Shifler18.1 Cast Irons 45318.1.1 Cast Iron Metallurgy 45418.1.2 Cast Iron Corrosion Behavior 45718.2 Carbon Steels 45818.2.1 Carbon Steel Chemistries 46018.2.1.1 Effects of Alloying Additions 46018.2.2 Surface Oxides/Corrosion Products 46318.2.3 Heat Treating 46418.2.4 Marine Steels 46818.3 Stainless Steels 47318.3.1 Stainless Steel Types 47418.3.1.1 Austenitic Stainless Steels 47418.3.1.2 Ferritic Stainless Steels 47518.3.1.3 Martensitic Stainless Steels 47818.3.1.4 Duplex Stainless Steels 47818.3.1.5 Precipitation-Hardening Stainless Steels 47918.3.2 Corrosion Behavior of Stainless Steels 47918.3.3 Marine Uses of Stainless Steels 48118.4 Nickel and Nickel Alloys 48118.4.1 Corrosion Resistant Nickel and Nickel Alloys 48318.4.2 High-temperature Nickel Alloys – Superalloys 48618.5 Aluminum and Aluminum Alloys 49018.5.1 Aluminum Alloy Familites 49018.5.2 Heat Treatment of Aluminum Alloys 49418.5.3 Corrosion Behavior of Aluminum Alloys 49618.6 Copper and Copper Alloys 49718.6.1 General Corrosion and Mechanical Properties 49718.6.2 Bronze Alloys 49818.6.3 Brasses 50218.6.4 Copper–Nickel Alloys 50318.7 Titanium and Titanium Alloys 50618.7.1 Chemistry and Metallurgy of Titanium Alloys 50718.7.2 General Corrosion Behavior 51018.8 Factors Affecting Alloy Corrosion Behavior in Marine Service 51018.8.1 Surface Properties and Processes 51018.8.1.1 Passivity 51018.8.2 Material Bulk Properties 51318.8.3 Joining Effects on Materials 51418.8.4 Cathodic Protection 518References 518Additional Reading and References 52519 Marine Coatings 527Charles G. Munger, Louis Vincent, and David A. Shifler19.1 Introduction 52719.2 Characteristics of a Ideal Marine Coating 52819.3 Coating Degradation and Failures 53219.4 Surface Preparation 53219.5 Coating Inspection, Selection, and Application for Controlling Corrosion 53619.6 Coatings for Marine Service 53919.6.1 Metallized Coatings 53919.6.1.1 Metal-Containing Primers 54219.6.1.2 Cadmium Plating 54319.6.1.3 Cadmium Options 54319.6.2 Organic Coatings 54419.6.2.1 Coating Thickness Measurements 54419.7 Types of Coatings for Marine Vessels 54519.7.1 Conversion Coatings 54719.7.1.1 Hexavalent Chromate Conversion Coatings 54719.7.1.2 Hexavalent Chromate Alternatives 54719.7.1.3 Phosphate Coatings 54819.7.2 Organic Coatings and Nanocomposites 54819.7.3 Shop Primers 54919.7.4 Universal Primers 55019.7.5 Zinc-Rich Coatings 55019.7.6 Organic Primers 55119.7.7 Tie-Coats 55219.7.8 Abrasion Resistant Coatings 55219.7.9 Cargo Tank Linings 55319.7.9.1 Tank Lining Chemical Resistance 55419.7.10 Bilge Coatings 55419.7.11 Ballast Tank Linings 55519.7.12 Cofferdam and Void Coatings 55819.7.13 Potable Water Tank Linings 55819.7.14 Cosmetic Finishes – Topside Area and Interior Living and Working Spaces 55919.7.15 Deck Coatings – Including Heli-Deck Surfaces 56019.7.16 Hull Coatings – Freeboard Area 56219.7.17 Maintenance Painting Programs 56319.8 Offshore Structures 563References 56520 Biofouling Control 573David A. Shifler20.1 The Nature of Biofouling 57320.2 Fouling Effects on Ships 57420.2.1 Control of Biofouling 57620.2.1.1 Biocidal Antifoulant Coatings 57620.3 Non-biocidal Antifoulant Methods and Coatings 57920.4 Maintenance, Monitoring, and Testing 582References 58721 Cathodic Protection 593James A. Ellor, David A. Shifler, and Robert A. Bardsley21.1 Theory 59321.2 Reference Cells 59621.3 Methods of Applying Cathodic Protection 59721.3.1 Cathodic Protection Using Sacrificial Anodes 59721.3.2 Impressed Current Cathodic Protection (ICCP) 60021.3.2.1 Impressed Current Anodes Materials 60121.3.2.2 Sacrificial Anodes 60221.3.2.3 Impressed Current Cathodic Protection 60421.4 Design Basics 60421.4.1 Calcareous Deposits and Impacts on Protection Criteria 60521.4.2 Polarization Characteristics Over Time 60721.4.3 Design Using Physical Scale Modeling 60821.4.4 Computer-Assisted Design 60921.4.5 Protective (Dielectric) Shields 60921.4.6 Protection Current Requirements 61021.4.7 Polarization Potential Criteria of Protection 61121.4.8 Automated Control Systems 61121.5 Cathodic Protection in Marine Service 61221.5.1 Small Boats and Large Commercial and Marine Vessels 61221.5.2 Offshore Structures 61521.5.3 Bridges, Wharves, and Jetties 61721.5.4 Marine Pipelines 62121.6 Concerns with the Use of Cathodic Protection 62321.6.1 Corrosion/Cathodic Protection Monitoring 624References 62622 Corrosion Monitoring in Seawater 633Sean Brossia22.1 Introduction 63322.2 Electrochemical Methods 63422.2.1 Linear Polarization Resistance 63422.2.2 Potential Measurements 63622.2.3 Electrochemical Impedance Spectroscopy 63722.2.4 Electrochemical Noise 64122.2.5 Electrochemical Frequency Modulation 64122.2.6 Wirebeam/Multielectrode Array Methods 64122.3 Non-Electrochemical Methods 64422.4 Challenges 64722.5 Applications 64822.6 Summary and Conclusions 649References 65023 Marine Fasteners 653David A. Shifler23.1 Introduction 65323.2 Failure Modes 65423.3 General Fastener Design 65523.4 Fastener Materials Selection 65623.4.1 Standards and Specifications 65623.4.2 Low-Alloy Steels 65923.4.3 Stainless Steels 65923.4.4 Aluminum Alloys 65923.4.5 Copper Alloys 66023.4.6 Nickel Alloys 66023.4.7 Titanium Alloys 66023.5 Fastener Behavior Above the Waterline 66123.6 Fastener Behavior in Submerged, Below the Waterline 66123.7 Corrosion Protection for Fasteners 662References 663Further Reading 66624 Marine and Offshore Piping Systems 667David A. Shifler24.1 Piping Systems 66724.1.1 Bilge System 66724.1.2 Ballast System 66724.1.3 Firefighting Systems 66824.1.4 Drainage Systems 66824.1.5 Fresh-Water Systems 66824.1.6 Fuel and Flammable Liquid Piping 66824.1.7 Ventilation Systems – Ships 66924.1.8 Hydrocarbon Piping (Oil and Gas) 66924.1.9 Vent System – Offshore 66924.1.10 Flare System 66924.1.11 Firewater Utility Piping 66924.1.12 Risers 67024.1.13 Subsea Piping 67024.2 Piping System Design 67124.3 Materials Selection 67224.4 Failure Modes of Piping Systems 67424.4.1 Uniform Corrosion 67424.4.2 Pitting and Crevice Corrosion 67524.4.3 Galvanic Corrosion 67724.4.4 Abrasion 68124.4.5 Erosion and Erosion Corrosion 68124.4.6 Variable Temperature Swings 68424.4.7 Wear and Impact 68424.4.8 Fatigue 68524.4.9 Water Hammer 68524.5 Corrosion Control Methods 686References 686Further Reading 68925 Corrosion Control and Preservation of Historic Marine Artifacts 691David A. Shifler25.1 Introduction 69125.2 Basic Conservation Procedures 69425.2.1 Laboratory Conservation Procedures 69525.3 Degradation, Corrosion, and Conservation of Marine Artifacts 69525.3.1 Corrosion and Conservation of Ferrous Alloys 69625.3.2 Corrosion and Conservation of Other Metals and Alloys 70025.3.2.1 Corrosion and Conservation of Copper Artifacts 70125.3.2.2 Corrosion and Conservation of Silver Artifacts 70125.3.3 Corrosion and Conservation of Lead, Tin, Pewter 702References 703Further Reading 705Marine Archaeology Conservation 705Index 707