Holdings: Introduction to corrosion science

Introduction to corrosion science:

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Bibliographic Details
Main Author:	McCafferty, E. (Author)
Format:	Book
Language:	English
Published:	New York [u.a.] Springer 2010
Subjects:	Korrosion Korrosionsschutz Elektrochemische Korrosion
Online Access:	Inhaltsverzeichnis
Physical Description:	XVI, 575 S. Ill., graph. Darst.
ISBN:	9781441904546

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adam_text	Titel: Introduction to Corrosion Science Autor: McCafferty, Edward Jahr: 2010 Contents 1 Societal Aspects of Corrosion............................... 1 We Live in a Metals-Based Society............................. I Why Study Corrosion?................................... 1 Corrosion and Human Life and Safety........................... I Economics of Corrosion .................................. 4 Corrosion and the Conservation of Materials........................ 5 The Study of Corrosion................................... 6 Corrosion Science vs, Corrosion Engineering....................... 8 Challenges for Today s Corrosion Scientist......................... 9 Problems .......................................... 10 References.......................................... 10 2 Getting Started on the Basics............................... 13 Introduction......................................... 13 What is Corrosion?.................................... 13 Physical Processes of Degradation............................ 13 Environmental^ Assisted Degradation Processes.................... 14 Electrochemical Reactions................................. 15 Half-Cell Reactions.................................... 15 Anodic Reactions..................................... 15 Cathodic Reactions.................................... 16 Coupled Electrochemical Reactions........................... 17 A Note About Atmospheric Corrosion.......................... 18 Secondary Effects of Cathodic Reactions........................ 19 Three Simple Properties of Solutions............................ 21 The Faraday and Faraday s Law .............................. 23 Units for Corrosion Rates.................................. 24 Uniform vs. Localized Corrosion.............................. 25 The Eight Forms of Corrosion.............................. 27 Problems .......................................... 28 References.......................................... 31 3 Charged Interfaces..................................... 33 Introduction......................................... 33 Electrolytes......................................... 33 The Interiorof an Electrolyte............................... 33 Interfaces.......................................... 35 Contents Eneountering an Interface................................ 35 The Solution/Air Interface................................ 36 The Metal/Solution Interface............................... 37 Metal Ions in Two Different Chemical Environments.................. 38 The Electrical Double Layer................................ 39 The Gouy?Chapman Model of the Electrical Double Layer.............. 40 The Electrostatic Potential and Potential Difference................... 40 The Stern Model of the Electrical Double Layer..................... 41 The Bockris?Devanathan?Müller Model of the Electrical Double Layer....... 42 Significance of the Electrical Double Layer to Corrosion................ 43 Electrode Potentials..................................... 44 The Potential Difference Across a Metal/Solution Interface............... 44 Relative Electrode Potentials............................... 45 The Electromotive Force Series............................. 46 Reference Electrodes for the Laboratory and the Field................... 48 Measurement of Electrode Potentials............................ 52 Problems .......................................... 53 References.......................................... 55 A Brief Review of Thermodynamics........................... 57 Introduction......................................... 57 Thermodynamie State Functions.............................. 57 Internal Energy...................................... 57 Entropy.......................................... 58 Enthalpy ......................................... 59 Helmholtz and Gibbs Free Energies........................... 59 Free Energy and Spontaneity............................... 60 Relationships Between Thermodynamie Functions................... 61 The Chemical Potential and Standard States........................ 63 More About the Chemical Potential........................... 63 A Note About Units for AG or AG........................... 64 The Free Energy and Electrode Potentials........................ 65 The Nernst Equation .................................... 66 Standard Free Energy Change and the Equilibrium Constant.............. 67 A Quandary - The Sign of Electrode Potentials...................... 68 Factors Affecting Electrode Potentials.......................... 69 Problems .......................................... 70 References.......................................... 72 Thermodynamics of Corrosion: Electrochemical Cells and Galvanic Corrosion.................................. 73 Introduction......................................... 73 Electrochemical Cells.................................... 73 Electrochemical Cells on the Same Surface....................... 75 Galvanic Corrosion..................................... 76 Galvanic Series...................................... 76 Cathodic Protection.................................... 79 TwoTypes of Metallic Coatings .............................. 80 Titanium Coatings on Steel: A Research Study..................... 82 Contents Protection Against Galvanic Corrosion........................... 83 Differential Concentration Cells . ,............................ 84 Metal Ion Concentration Cells.............................. 84 Oxygen Concentration Cells............................... 86 The Evans Water Drop Experiment ........................... 88 Waterline Corrosion ................................... 88 Crevice Corrosion: A Preview.............................. 89 Problems .......................................... 89 References.......................................... 93 Thermodynamics of Corrosion: Pourbaix Diagrams.................. 95 Introduction......................................... 95 Pourbaix Diagram for Aluminum.............................. 96 Construction of the Pourbaix Diagram for Aluminum.................. 96 Comparison of Thermodynamie and Kinetic Data for Aluminum............ 101 Pourbaix Diagram for Water................................ 101 Pourbaix Diagrams for Other Metals............................ 103 Pourbaix Diagram forZinc................................ 103 Pourbaix Diagram for Iron................................ 103 Pourbaix Diagrams for Additional Metals........................ 106 Applications of Pourbaix Diagrams to Corrosion...................... 108 Limitations of Pourbaix Diagrams............................. 111 Pourbaix Diagrams for Alloys.............................. 111 Pourbaix Diagrams at Elevated Temperatures ....................... 112 Problems .......................................... 114 References.......................................... 116 Kinetics of Corrosion................................... 119 Introduction......................................... 119 Units for Corrosion Rates ................................ 119 Methodsof Determining Corrosion Rates ......................... 119 Weight Loss Method................................... 120 Weight Gain Method................................... 120 Chemical Analysis of Solution.............................. 121 Gasometric Techniques.................................. 122 Thickness Measurements................................. 124 Electrical Resistance Method............................... 124 Inert Marker Method................................... 124 Electrochemical Techniques............................... 126 Electrochemical Polarization................................ 127 Anodic and Cathodic Polarization............................ 127 Visualization of Cathodic Polarization.......................... 127 Visualization of Anodic Polarization........................... 128 Ohmic Polarization.................................... 130 Electrode Kinetics for Activation Polarization....................... 131 Absolute Reaction Rate Theory ............................. 131 Electrode Kinetics for Non-Corroding Metals...................... 132 How to Plot Polarization Curves?............................ 136 The Tafel Equation.................................... 138 Contents Reversible and Irreversible Potentials.......................... 139 Mixed Potential Theory (Wagner and Traud) ...................... 140 Electrode Kinetic Parameters............................... 144 Applications of Mixed Potential Theory.......................... 146 Metals in Acid Solutions................................. 146 Tafel Extrapolation.................................... 148 Verification of Corrosion Rates Obtained by Tafel Extrapolation............ 150 Cathodic Protection of Iron in Acids........................... 150 Effect of the Cathodic Reaction ............................. 154 Effect of Cathode Area on Galvanic Corrosion ..................... 154 Multiple Oxidation-Reduction Reactions........................ 156 Anodic or Cathodic Control............................... 158 The Linear Polarization Method (Stern and Geary) .................... 159 Advantages and Possible Errors for the Linear Polarization Technique......... 162 Applications of the Linear Polarization Technique ................... 163 Small-Amplitude Cyclic Voltammetry.......................... 164 Experimental Techniques for Determination of Polarization Curves............ 165 Electrode Samples.................................... 165 Electrode Holders..................................... 166 Electrochemical Cells .................................. 167 Instrumentation and Procedures............................. 168 Problems .......................................... 169 References.......................................... 173 Concentration Polarization and Diffusion........................ 177 Introduction......................................... 177 Where Oxygen Reduction Occurs............................ 177 Concentration Polarization in Current Density-Potential Plots............. 178 Solubility and Diffusion................................... 179 Solubility of Oxygen in Aqueous Solutions....................... 179 Fick s First Law of Diffusion............................... 181 Diffusion and Random Walks .............................. 183 Electrode Kinetics for Concentration Polarization..................... 186 Concentration Profile Near an Electrode Surface .................... 186 Limiting Diffusion Current Density........................... 187 Diffusion Layer vs. The Diffuse Layer.......................... 189 Current-Potential Relationship for Concentration Polarization............. 189 Wagner-Traud Theory for Concentration Polarization.................. 191 Effect of Environmental Factors on Concentration Polarization and Corrosion...... 192 Effect of Oxygen Concentration............................. 193 Effect of Solution Velocity................................ 194 Effect of Temperature .................................. 196 Further Applications of Concentration Polarization Curves................ 197 Cathodic Protection.................................... 197 Area Effects in Galvanic Corrosion ........................... 199 Linear Polarization.................................... 199 Concentration Polarization in Acid Solutions...................... 200 Combined Activation and Concentration Polarization.................. 202 Contents xi The Rotating Disc Electrode............................... 202 Problems .......................................... 205 References.......................................... 208 9 Passivity .......................................... 209 Introduction......................................... 209 Aluminum: An Example................................. 209 What is Passivity? .................................... 210 Early History of Passivity ................................ 210 Thicknessof Passive Oxide Films............................ 210 Purpose of This Chapter................................. 211 Electrochemical Basis for Passivity............................. 211 Theories of Passivity.................................... 215 Adsorption Theory.................................... 215 Oxide Film Theory.................................... 216 Film Sequence Theory.................................. 218 Surface Analysis Techniques for the Examination of Passive Films............ 218 X-ray Photoelectron Spectroscopy (XPS)........................ 220 X-ray Absorption Spectroscopy............................. 222 Scanning Tunneling Microscopy............................. 223 Models for the Passive Oxide Film on Iron......................... 224 Bilayer Model ...................................... 224 Hydrous Oxide Model.................................. 227 Bipolar-Fixed Charge Model............................... 228 Spinel/Defect Model................................... 229 What Do These Various Models Mean?......................... 230 Passive Oxide Films on Aluminum............................. 230 Air-Formed Oxide Films................................. 231 Films Formed in Aqueous Solutions........................... 231 Properties of Passive Oxide Films ............................. 232 Thickness......................................... 233 Electronic and Ionic Conductivity............................ 233 Chemical Stability.................................... 233 Mechanical Properties.................................. 234 Structure of Passive Films................................ 235 Passivity in Binary Alloys.................................. 237 Electron Configuration Theory.............................. 238 Oxide Film Properties.................................. 241 Percolation Theory.................................... 242 Graph Theory Model................................... 243 Passivity in Stainless Steels................................. 249 Electrochemical Aspects................................. 250 Composition of Passive Films on Stainless Steels.................... 252 Passivity by Alloying with Noble Metals.......................... 254 Anodic Protection...................................... 255 Problems .......................................... 257 References.......................................... 260 xü Contents 10 Crevice Corrosion and Pitting .............................. 263 Introduction......................................... 263 Crevice Corrosion...................................... 263 Initiation of Crevice Corrosion.............................. 264 Propagation of Crevice Corrosion............................ 269 Crevice Corrosion Testing................................ 272 Area Effects in Crevice Corrosion............................ 274 Protection Against Crevice Corrosion.......................... 275 Pitting............................................ 277 Critical Pitting Potential................................. 278 Experimental Determination of Pitting Potentials.................... 280 Effect of Chloride Ions on the Pitting Potential ..................... 282 Effect of Inhibitors on the Pitting Potential ....................... 283 Mechanism of Pit Initiation ............................... 283 Mechanism of Pit Propagation.............................. 286 Protection Potential.................................... 288 Metastable Pits and Repassivation............................ 290 Experimental Pourbaix Diagrams for Pitting....................... 291 Effect of Molybdenum on the Pitting of Stainless Steels ................ 293 Effect of Sulfide Inclusions on the Pitting of Stainless Steels.............. 294 Effect of Temperature .................................. 294 Protection Against Pitting................................ 296 Pitting of Aluminum .................................... 297 Occluded Corrosion Cells.................................. 300 Occluded Corrosion Cell (OCC) on Iron......................... 301 Occluded Corrosion Cells on Copper and Aluminum.................. 303 Differences Between Pitting and Crevice Corrosion................... 306 Detection of Corrosion Pits................................. 306 Problems .......................................... 308 References.......................................... 311 11 Mechanically Assisted Corrosion............................. 315 Introduction......................................... 315 Stress-Corrosion Cracking................................. 318 Mechanical Metallurgy.................................. 318 Characteristics of Stress-Corrosion Cracking...................... 319 Stages of Stress-Corrosion Cracking........................... 320 Fracture Mechanics and SCC............................... 323 SCC Testing ....................................... 331 Interpretation of SCC Test Data............................. 334 Metallurgical Effects in SCC............................... 335 Environmental Effects on SCC.............................. 336 Mechanisms of SCC................................... 339 Protection Against Stress-Corrosion Cracking...................... 345 Corrosion Fatigue...................................... 346 Corrosion Fatigue Data.................................. 347 Protection Against Corrosion Fatigue.......................... 348 Cavitation Corrosion .................................... 349 Contents iü Erosion Corrosion and Fretting Corrosion......................... 352 Problems .......................................... 353 References.......................................... 354 12 Corrosion Inhibitors.................................... 357 Introduction.......................................... 357 Types of Inhibitors ..................................... 359 Acidic Solutions....................................... 360 Chemisorption of Inhibitors............................... 361 Effect of Inhibitor Concentration............................. 362 Chemical Factors in the Effectiveness of Chemisorbed Inhibitors............ 363 Involvement of Water................................... 367 Competitive vs. Co-operative Adsorption........................ 369 Effect of the Electrical Double Layer.......................... 370 The Potential of Zero Charge............................... 372 Effect of Molecular Structure .............................. 373 Adsorption Isotherms................................... 376 Nearly Neutral Solutions.................................. 379 Effect of Oxide Films................................... 379 Chelating Compounds as Corrosion Inhibitors...................... 380 Chromates and Chromate Replacements......................... 381 Inhibition of Localized Corrosion.............................. 382 Pitting Corrosion..................................... 382 Crevice Corrosion .................................... 386 Stress-Corrosion Cracking and Corrosion Fatigue.................... 387 New Approaches to Corrosion Inhibition.......................... 389 Biological Molecules................................... 390 Langmuir-Blodgett Films and Self-assembled Monolayers............... 393 Vapor-Phase Inhibitors................................... 396 Problems .......................................... 398 References.......................................... 400 13 Corrosion Under Organic Coatings ........................... 403 Introduction......................................... 403 Paints and Organic Coatings ................................ 404 Underfilm Corrosion .................................... 405 Water Permeation into an Organic Coating ....................... 406 Permeation of Oxygen and Ions into an Organic Coating................ 410 Breakdown of an Organic Coating............................ 411 Adhesion of Organic Coatings.............................. 412 Improved Corrosion Prevention by Coatings....................... 416 Filiform Corrosion ..................................... 417 Corrosion Tests for Organic Coatings............................ 419 Accelerated Tests..................................... 419 Cathodic Delamination.................................. 419 AC Impedance Techniques - A Brief Comment..................... 422 Recent Directions and New Challenges........................... 422 Problems .......................................... 423 References.......................................... 425 xjv Contents 14 AC Impedance....................................... 427 Introduction......................................... 427 Relaxation Processes................................... 427 Experimental Setup.................................... 429 Complex Numbers and AC Circuit Analysis....................... 430 The Metal/Solution Interface................................ 431 Impedance Analysis................................... 432 Additional Methods of Plotting Impedance Data .................... 434 Multiple Time Constants and the Effect of Diffusion.................. 436 Kramers-Kronig Transforms............................... 437 Application to Corrosion Inhibition........................... 438 Organic Coatings...................................... 441 Oxide Films and Surface Treatments............................ 446 Concluding Remarks.................................... 449 Problems .......................................... 449 References.......................................... 451 15 High-Temperature Gaseous Oxidation.......................... 453 Introduction......................................... 453 Thermodynamics of High-Temperature Oxidation..................... 453 Ellingham Diagrams................................... 454 Equilibrium Pressure of Oxygen............................. 455 Theory of High-Temperature Oxidation .......................... 456 Oxidation Rate Laws.................................... 457 Linear Rate Law..................................... 458 Parabolic Rate Law.................................... 459 Logarithmic Rate Law.................................. 460 Comparison of Rate Laws................................ 460 The Wagner Mechanism and the Parabolic Rate Law.................. 460 Effect of Temperature on the Oxidation Rate ...................... 463 Defect Nature of Oxides .................................. 463 Semiconductor Nature of Oxides............................. 465 Hauffe Rules for Oxidation................................ 466 Effect of Oxygen Pressure on Parabolic Rate Constants................. 471 Non-uniformity of Oxide Films............................... 472 Protective vs. Non-protective Oxides............................ 473 Pilling-Bedworth Ratio ................................. 473 Properties of Protective High-Temperature Oxides ................... 473 Problems .......................................... 474 References........................................... 475 16 Selected Topics in Corrosion Science........................... 477 Introduction......................................... 477 Electrode Kinetics of Iron Dissolution in Acids ...................... 477 Bockris-Kelly Mechanism................................ 478 Heusler Mechanism ................................... 480 Reconciliation of the Two Mechanisms......................... 481 Additional Work on Electrode Kinetics......................... 482 Distribution of Current and Potential............................ 483 Contents xv Laplace s Equation.................................... 483 Circular Corrosion Cells................................. 483 Parametric Study..................................... 486 Application to the Experiments of Rozenfeld and Pavlutskaya............. 488 Large Structures and Scaling Rules............................. 489 Modelingof the Cathodic Protection System ofa Ship................. 491 Scaling Rules....................................... 492 Acid-Base Properties of Oxide Films............................ 494 Surface Hydroxyl Groups ................................ 494 Nature of Acidic and Basic Surface Sites........................ 495 Isoelectric Points of Oxides ............................... 495 Surface Charge and Pitting................................ 497 Pitting Potential of Aluminum as a Function of pH................... 498 Surface Modifikation by Directed Energy Beams...................... 499 Ion Implantation and Related Processes......................... 499 Applications of Ion Implantation............................. 501 Laser-Surface Processing Techniques.......................... 505 Applications ofLaser-Surface Processing........................ 507 Comparison of Ion Implantation and Laser-Surface Processing............. 509 Problems .......................................... 510 References.......................................... 512 17 Beneficial Aspects of Corrosion.............................. 515 Introduction......................................... 515 Rust Is Beautiful..................................... 515 Copper Patinas Are Also Beautiful............................ 515 Cathodic Protection.................................... 517 Electrochemical Machining ............................... 517 Metal Cleaning...................................... 517 Etching.......................................... 517 Batteries ......................................... 517 Passivity ......................................... 517 Anodizing......................................... 518 Titanium Jewelry and Art................................. 518 Caution to Inexperienced Artisans:............................. 518 References.......................................... 518 Answers to Selected Problems ................................ 521 Chapter 2.......................................... 521 Chapter 3.......................................... 521 Chapter 4.......................................... 522 Chapter 5.......................................... 522 Chapter 6.......................................... 523 Chapter 7.......................................... 524 Chapter 8.......................................... 524 Chapter 9.......................................... 524 Chapter 10.......................................... 525 Chapter 11.......................................... 526 Chapter 12.......................................... 526 xvi Contents Chapter 13.......................................... 527 Chapter 14.......................................... 528 Chapter 15.......................................... 528 Chapter 16.......................................... 528 Appendix A: Some Properties of Various Elemental Metals................ 531 Appendix B: Thermodynamie Relationships for Use in Constructing Pourbaix Diagrams at High Temperatures............................. 533 References.......................................... 534 Appendix C: Relationship Between the Rate Constant and the Activation Energy for a Chemical Reaction............................. 535 Appendix D: Random Walks in Two Dimensions...................... 537 Appendix E: Uhlig s Explanation for the Flade Potential on Iron............. 541 Appendix F: Calculation of the Randic Index X{G) for the Passive Film on Fe-Cr AUoys...................................... 543 References.......................................... 545 Appendix G: Acid Dissociation Constants pKa of Bases and the Base Strength ..... 547 Appendix H: The Langmuir Adsorption Isotherm..................... 549 Appendix I: The Temkin Adsorption Isotherm....................... 551 Appendix J: The Temkin Adsorption Isotherm for a Charged Interface......... 553 Appendix K: Effect of Coating Thickness on the Transmission Rate of a Molecule Permeating Through a Free-Standing Organic Coating........ 557 Appendix L: The Impedance for a Capacitor........................ 559 Reference.......................................... 559 Appendix M: Use of L HospitaPs Rule to Evaluate \|Z\| for the Metal/Solution Interface for Large Values of Angular Frequency w.................. 561 Appendix N: Derivation of the Are Chord Equation for Cole-Cole plots........ 563 References.......................................... 565 Appendix O: Laplace s Equation .............................. 567 Reference.......................................... 569 Index.............................................. 571
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publisher	Springer
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spelling	McCafferty, E. Verfasser aut Introduction to corrosion science E. McCafferty New York [u.a.] Springer 2010 XVI, 575 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Korrosion (DE-588)4032518-0 gnd rswk-swf Korrosionsschutz (DE-588)4032522-2 gnd rswk-swf Elektrochemische Korrosion (DE-588)4197345-8 gnd rswk-swf Elektrochemische Korrosion (DE-588)4197345-8 s DE-604 Korrosion (DE-588)4032518-0 s Korrosionsschutz (DE-588)4032522-2 s Erscheint auch als Online-Ausgabe 978-1-4419-0455-3 HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=020196141&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis
spellingShingle	McCafferty, E. Introduction to corrosion science Korrosion (DE-588)4032518-0 gnd Korrosionsschutz (DE-588)4032522-2 gnd Elektrochemische Korrosion (DE-588)4197345-8 gnd
subject_GND	(DE-588)4032518-0 (DE-588)4032522-2 (DE-588)4197345-8
title	Introduction to corrosion science
title_auth	Introduction to corrosion science
title_exact_search	Introduction to corrosion science
title_full	Introduction to corrosion science E. McCafferty
title_fullStr	Introduction to corrosion science E. McCafferty
title_full_unstemmed	Introduction to corrosion science E. McCafferty
title_short	Introduction to corrosion science
title_sort	introduction to corrosion science
topic	Korrosion (DE-588)4032518-0 gnd Korrosionsschutz (DE-588)4032522-2 gnd Elektrochemische Korrosion (DE-588)4197345-8 gnd
topic_facet	Korrosion Korrosionsschutz Elektrochemische Korrosion
url	http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=020196141&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA
work_keys_str_mv	AT mccaffertye introductiontocorrosionscience

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