Electro-Chemo-Mechanical Properties of Solid Electrode Surfaces

Electro-Chemo-Mechanical Properties of Solid Electrode Surfaces
Masahiro Seo
Contents
1 Surface Thermodynamics of Solid Electrode . 1
1.1 Introduction . 1
1.2 Definition of Surface Phase 2
1.3 Surface Excess Quantities . 4
1.4 Surface Plastic and Elastic Strains . 7
1.5 Major Parameters of Surface Thermodynamics 8
1.6 Surface Tension and Surface Stress 13
1.7 Gibbs–Duhem Equation of Solid Surface 16
1.8 Electrified Interface and Electrocapillarity . 18
1.9 Electrocapillary Curves of Liquid and Solid Metal Electrodes . 24
1.10 Surface Stress versus Potential Curve of Solid Metal
Electrode . 28
Appendix 1: Derivation of the Tensor Equivalent of the Shuttleworth
Equation 33
Appendix 2: Calculation of the Magnitude of Surface Elastic
Strain from the Curvature Change of Cantilever Bending . 36
References . 37
2 Methods for Investigating Electro-Chemo-Mechanical
Properties of Solid Electrode Surfaces . 39
2.1 Introduction . 39
2.2 Piezoelectric Detection of Differential Surface Stress . 40
2.3 Cantilever Bending Method for Measurement of Changes
in Surface Stress 48
2.3.1 Relationship between Surface Stress and Curvature
of Cantilever . 48
2.3.2 Optical Detection of Curvature 51
vii2.4 Elastic Deformation of Metal Electrode Associated
with Surface Stress 59
2.5 Dilatometric Detection of Strain Change for Nano-Porous
Metal Electrode 63
References . 65
3 Potential- or Adsorbate-Induced Changes in Surface Stress
of Solid Metal Electrode, and Surface Stress versus Surface
Charge Density or Potential versus Surface Elastic Strain 67
3.1 Introduction . 67
3.2 Surface Reconstruction . 68
3.2.1 Au (100) Surface 70
3.2.2 Au (111) Surface 74
3.2.3 Roles of Surface Stress in Surface Reconstruction 77
3.3 Adsorption of Electrolyte Anions 78
3.3.1 Au (111) Electrode in Acid Solutions Containing
ClO4−, SO42−, and Cl− 78
3.3.2 Au (111) Electrode in Perchlorate Solution Containing
Iodide Ions 81
3.4 Surface Stress versus Surface Charge Density or Potential
versus Surface Elastic Strain . 84
3.4.1 Surface Stress–Surface Charge Density
Coefficient fg;q 84
3.4.2 Determination of fg;q by Dynamic Stress Analysis
Combined with Electrochemical Impedance
Spectroscopy . 85
3.4.3 Potential–Surface Elastic Strain Coefficient fE;e 88
3.4.4 Sign-Reversal of fg;q in the Hydrogen
Adsorption/Desorption Region or in the Oxide
Formation/Reduction Region . 92
3.4.5 Origin of Sign-Reversal of fg;q 98
References . 100
4 Changes in Surface Stress Associated with Underpotential
Deposition and Surface Alloying 103
4.1 Introduction . 103
4.2 Underpotential Deposition (UPD) . 104
4.2.1 UPD and Work Function 104
4.2.2 Equilibrium Potential of UPD and Adsorption
Isotherm 107
viii Contents4.3 Changes in Surface Stress during UPD . 108
4.3.1 Pb-UPD on Au (111) . 109
4.3.2 Bi-UPD on Au (111) . 115
4.3.3 Cu-UPD on Au (111) . 119
4.3.4 Pd-UPD on Au (111) . 128
4.4 Surface Alloying 132
References . 135
5 Controversy of Thermodynamics Associated with Surface Stress
and Surface Tension of Solid Electrode 139
5.1 Introduction . 139
5.2 On Homogeneous Nature of the Thermodynamic Functions
of Solid Electrode . 140
5.3 Incompatibility of Shuttleworth Equation with Hermann’s
Mathematical Structure of Thermodynamics 143
5.4 Thermodynamic Issues Associated with Shuttleworth Equation
and with Surface Stress Measurement by a Cantilever Bending
Method 145
References . 146
6 Stresses of Anodic Oxide Films Grown on Metal Electrode . 149
6.1 Introduction . 149
6.2 High Field Model for Growth of Anodic Oxide Film . 150
6.3 Pilling–Bedworth Ratio . 154
6.4 Transport Number of Mobile Ion in Anodic Oxide Film
and Stress Generation 156
6.5 Criterion for Stress Generation by Nelson and Oriani . 158
6.5.1 Stress Generation during Anodic Oxidation of Al 160
6.5.2 Stress Generation during Anodic Oxidation of Ti . 161
6.6 Compressive Stress due to Electrostriction . 166
6.7 Residual Stress of Substrate Metal . 168
6.8 Cathodic Polarization of Anodic Oxide Film . 170
6.9 Plastic Flow of Porous Anodic Oxide Film 172
References . 176
7 Nano-Mechanical Properties of Solid Surfaces Obtained
by Nano-Indentation . 179
7.1 Introduction . 179
7.2 Fundamentals of Nano-Indentation . 180
7.3 Nano-Mechanical Properties of Solid Surfaces Obtained
by Nano-Indentation in Air 187
7.3.1 Single Crystal Gold Surfaces . 187
7.3.2 Metal Oxide Surfaces . 190
7.3.3 Indentation Size Effect (ISE) in MgO . 192
7.3.4 Anodic Oxide Films on Metals 199
Contents ix7.4 Nano-Mechanical Properties of Passive Metal Surfaces
Obtained by Electrochemical Nano-Indentation 201
7.4.1 Passive Single Crystal Fe (100) and (110) Surfaces
in Solution 202
7.4.2 Effect of Chromate Treatment on Nano-Mechanical
Properties of Passive Fe Surfaces 205
References . 21
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