Surface Chemistry of Aqueous Corrosion Processes (eBook)

Dr. Edward McCafferty, formerly of the Naval Research Laboratory, is currently a consultant in Alexandria, VA.  He has published extensively in the fields of corrosion science and surface chemistry.  Dr. McCafferty's interests include corrosion and corrosion protection, localized corrosion, corrosion inhibition, models of passivity and its breakdown, oxide surfaces, surface modification techniques such as ion implantation and laser-surface processing, and the adhesion of organic polymers. Dr. McCafferty is a Fellow of the Electrochemical Society and is the 2007 recipient of the H. H. Uhlig Award of the Electrochemical Society for excellence in corrosion research.  Dr. McCafferty is also Past Chairman of the Corrosion Division of the Electrochemical Society.  He has received the Jerome Kruger Award in Corrosion Science, Baltimore-Washington Chapter of NACE (2003) and the Victor K. LaMer Award of the American Chemical Society (1971). Dr. McCafferty holds a B.S. in Chemistry from Wilkes College, an M.S. and Ph.D in Chemistry from Lehigh University, and an M.S. in Applied Mathematics from Johns Hopkins University.  He has been a Visiting Scientist, Department of Chemistry and the Center for Adhesive and Sealant Science, Virginia Tech University (1996-1997) and a Robert A. Welch Postdoctoral Fellow at the University of Texas with Prof. Norman Hackerman  (1968-1970).  He has also had industrial experience as a Research Engineer at the Bethlehem Steel Corporation (1955-1959).

Preface 6
Contents 7
1 Acid-Base Properties of Surface Oxide Films 10
Introduction 10
Surface Hydroxyl Groups 10
Nature of Acidic and Basic Surface Sites 12
Determination of Isoelectric Points of Metal Oxides and Oxide Films 13
Streaming Potential Measurement 14
Contact Angle Measurements 14
Surface Reaction Method of Simmons and Beard 17
Ionic Interaction Model of Parks [26] 19
XPS Correlation Method 21
Measurement of Near-Surface Forces 24
Numerical Values of Isoelectric Points 24
Surface Charge of Oxide Films 25
Pitting of Aluminum 25
Adsorption of Cl2212 on Aluminum 26
Electrode Kinetics of Pit Initiation on Aluminum 27
Pitting Potential of Aluminum as a Function of PH 29
Pitting Potential of Aluminum as a Function of Cl2212 Concentration 30
Acid-Base Interactions in Metal/Polymer Adhesion 32
Introduction 32
Theories of Polymer Adhesion 32
Acid-Base Nature of Organic Polymers 33
Characterization of the Acid-Base Properties of Polymers 34
Metal/Polymer Adhesion Tests 37
Wet Adhesion 40
Acid-Base Effects in Corrosion Inhibition 40
General Effect of Oxide Films 40
Mechanisms of Interaction with Oxide Films 42
Interaction of Inhibitors with Hydroxylated Oxide Films 42
Chelating Compounds as Corrosion Inhibitors 42
Hard and Soft Acids and Bases 44
Interaction of Cations with Oxide Films 47
Relationship Between the Isoelectric Point (pHpzc) and the Potential of Zero Charge (Epzc) for Passive Metals 48
General Remarks 48
Measurement of Potentials of Zero Charge for Passive Metals 50
Potential Drop in the Metal/Oxide/Electrolyte System 50
Space Charge Side of the Oxide/Solution Interface 51
Solution Side of the Oxide/Solution Interface 53
Numerical Evaluation 57
Summary 58
References 58
2 Capillarity and Corrosion 64
Introduction 64
Capillarity 64
Application to Organic Coatings 66
Young and Laplace Equation 68
Force Between Glass Plates 69
Application to Poultice Corrosion 69
Application to White Rusting 71
References 71
3 A Recent Model of Passivity for Fe-Cr and Fe-Cr-Ni Alloys 72
Fe-Cr Alloys 72
Fe-Cr-Ni Alloys 75
References 78
4 Uptake of Chloride Ions and the Pitting of Aluminum 80
Introduction 80
Sequence of Steps 80
XPS Studies 81
Formation of Blisters 82
Localized Corrosion Cells 83
References 84
5 Formation of Water Films on the Iron Oxide Surface 85
Introduction 85
Experimental 85
Results and Discussion 86
Formation of Liquid-Like Layers 89
References 91
6 Corrosion Inhibition by Fluorinated Aliphatic Compounds 92
Introduction 92
Fluorinated Carboxylic Acids and Amines 92
Experimental Results 94
Suggestions for Further Work 96
References 96