4.3 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
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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
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