This book deals with the electro-chemo-mechanical properties characteristic of and unique to solid electrode surfaces, covering interfacial electrochemistry and surface science.
Electrochemical reactions such as electro-sorption, electro-deposition or film growth on a solid electrode induce changes in surface stress or film stress that lead to transformation of the surface phase or alteration of the surface film. The properties of solid electrode surfaces associated with the correlation between electrochemical and mechanical phenomena are named “electro-chemo-mechanical properties”.
The book first derives the surface thermodynamics of solid electrodes as fundamentals for understanding the electro-chemo-mechanical properties. It also explains the powerful techniques for investigating the electro-chemo-mechanical properties, and reviews the arguments for derivation of surface thermodynamics of solid electrodes. Further, based on current experimental findings and theories, it discusses the importance of the contribution of surface stress to the transformation of surface phases, such as surface reconstruction and underpotential deposition in addition to the stress evolution during film growth and film reduction. Moreover, the book describes the nano-mechanical properties of solid surfaces measured by nano-indentation in relation to the electro-chemo-mechanical properties.
This book makes a significant contribution to the further development of numerous fields, including electrocatalysis, materials science and corrosion science.
Author(s): Masahiro Seo
Edition: 1
Publisher: Springer Singapore
Year: 2020
Language: English
Pages: 216
City: Singapore
Tags: Electro-Chemo-Mechanical Properties Surface Thermodynamics of Solid Electrode Surface Stress and Surface Tension Underpotential Deposition and Surface Alloying Mechanical Properties of Thin Film
Preface
Contents
1 Surface Thermodynamics of Solid Electrode
1.1 Introduction
1.2 Definition of Surface Phase
1.3 Surface Excess Quantities
1.4 Surface Plastic and Elastic Strains
1.5 Major Parameters of Surface Thermodynamics
1.6 Surface Tension and Surface Stress
1.7 Gibbs–Duhem Equation of Solid Surface
1.8 Electrified Interface and Electrocapillarity
1.9 Electrocapillary Curves of Liquid and Solid Metal Electrodes
1.10 Surface Stress versus Potential Curve of Solid Metal Electrode
Appendix 1: Derivation of the Tensor Equivalent of the Shuttleworth Equation
Appendix 2: Calculation of the Magnitude of Surface Elastic Strain from the Curvature Change of Cantilever Bending
References
2 Methods for Investigating Electro-Chemo-Mechanical Properties of Solid Electrode Surfaces
2.1 Introduction
2.2 Piezoelectric Detection of Differential Surface Stress
2.3 Cantilever Bending Method for Measurement of Changes in Surface Stress
2.3.1 Relationship between Surface Stress and Curvature of Cantilever
2.3.2 Optical Detection of Curvature
2.4 Elastic Deformation of Metal Electrode Associated with Surface Stress
2.5 Dilatometric Detection of Strain Change for Nano-Porous Metal Electrode
References
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
3.1 Introduction
3.2 Surface Reconstruction
3.2.1 Au (100) Surface
3.2.2 Au (111) Surface
3.2.3 Roles of Surface Stress in Surface Reconstruction
3.3 Adsorption of Electrolyte Anions
3.3.1 Au (111) Electrode in Acid Solutions Containing ClO4−, SO42−, and Cl−
3.3.2 Au (111) Electrode in Perchlorate Solution Containing Iodide Ions
3.4 Surface Stress versus Surface Charge Density or Potential versus Surface Elastic Strain
3.4.1 Surface Stress–Surface Charge Density Coefficient ζg,q
3.4.2 Determination of ζg,q by Dynamic Stress Analysis Combined with Electrochemical Impedance Spectroscopy
3.4.3 Potential–Surface Elastic Strain Coefficient ζE,ε
3.4.4 Sign-Reversal of ζg,q in the Hydrogen Adsorption/Desorption Region or in the Oxide Formation/Reduction Region
3.4.5 Origin of Sign-Reversal of ζg,q
References
4 Changes in Surface Stress Associated with Underpotential Deposition and Surface Alloying
4.1 Introduction
4.2 Underpotential Deposition (UPD)
4.2.1 UPD and Work Function
4.2.2 Equilibrium Potential of UPD and Adsorption Isotherm
4.3 Changes in Surface Stress during UPD
4.3.1 Pb-UPD on Au (111)
4.3.2 Bi-UPD on Au (111)
4.3.3 Cu-UPD on Au (111)
4.3.4 Pd-UPD on Au (111)
4.4 Surface Alloying
References
5 Controversy of Thermodynamics Associated with Surface Stress and Surface Tension of Solid Electrode
5.1 Introduction
5.2 On Homogeneous Nature of the Thermodynamic Functions of Solid Electrode
5.3 Incompatibility of Shuttleworth Equation with Hermann’s Mathematical Structure of Thermodynamics
5.4 Thermodynamic Issues Associated with Shuttleworth Equation and with Surface Stress Measurement by a Cantilever Bending Method
References
6 Stresses of Anodic Oxide Films Grown on Metal Electrode
6.1 Introduction
6.2 High Field Model for Growth of Anodic Oxide Film
6.3 Pilling–Bedworth Ratio
6.4 Transport Number of Mobile Ion in Anodic Oxide Film and Stress Generation
6.5 Criterion for Stress Generation by Nelson and Oriani
6.5.1 Stress Generation during Anodic Oxidation of Al
6.5.2 Stress Generation during Anodic Oxidation of Ti
6.6 Compressive Stress due to Electrostriction
6.7 Residual Stress of Substrate Metal
6.8 Cathodic Polarization of Anodic Oxide Film
6.9 Plastic Flow of Porous Anodic Oxide Film
References
7 Nano-Mechanical Properties of Solid Surfaces Obtained by Nano-Indentation
7.1 Introduction
7.2 Fundamentals of Nano-Indentation
7.3 Nano-Mechanical Properties of Solid Surfaces Obtained by Nano-Indentation in Air
7.3.1 Single Crystal Gold Surfaces
7.3.2 Metal Oxide Surfaces
7.3.3 Indentation Size Effect (ISE) in MgO
7.3.4 Anodic Oxide Films on Metals
7.4 Nano-Mechanical Properties of Passive Metal Surfaces Obtained by Electrochemical Nano-Indentation
7.4.1 Passive Single Crystal Fe (100) and (110) Surfaces in Solution
7.4.2 Effect of Chromate Treatment on Nano-Mechanical Properties of Passive Fe Surfaces
References
