Electrochemistry for Materials Science

By: Walter Plieth

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Hardcover | 17 December 2007

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432 Pages

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This book introduces the principles of electrochemistry with a special emphasis on materials science. This book is clearly organized around the main topic areas comprising electrolytes, electrodes, development of the potential differences in combining electrolytes with electrodes, the electrochemical double layer, mass transport, and charge transfer, making the subject matter more accessible.
In the second part, several important areas for materials science are described in more detail. These chapters bridge the gap between the introductory textbooks and the more specialized literature. They feature the electrodeposition of metals and alloys, electrochemistry of oxides and semiconductors, intrinsically conducting polymers, and aspects of nanotechnology with an emphasis on the codeposition of nanoparticles.
This book provides a good introduction into electrochemistry for the graduate student. For the research student as well as for the advanced reader there is sufficient information on the basic problems in special chapters. The book is suitable for students and researchers in chemistry, physics, engineering, as well as materials science.

- Introduction into electrochemistry
- Metal and alloy electrodeposition
- Oxides and semiconductors, corrosion
- Intrinsically conducting polymers
- Codeposition of nanoparticles, multilayers

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Non-Fiction Science Chemistry Analytical Chemistry Engineering & Technology Mechanical Engineering & Materials Materials Science Physical Chemistry Electrochemistry & Magnetochemistry

List of Symbols	p. xi
Preface	p. xxi
Electrolytes	p. 1
Liquid Electrolyte Solutions	p. 1
Ionic Melts	p. 6
Alkali halide melts	p. 6
Glass forming molten salts	p. 7
Ionic liquids	p. 8
Ionic Conductance in Polymers	p. 10
Polymer electrolytes	p. 10
Gel polymer electrolytes	p. 12
Ion exchanging polymer electrolytes	p. 13
Ionic Conductance in Solids	p. 13
Crystal defects	p. 13
Intrinsic disorder	p. 16
Extrinsic disorder	p. 18
Disorder in sub-lattices	p. 19
Transport by defects	p. 23
Ion conducting glasses	p. 23
Mixed ionic and electronic conductance	p. 24
Structure and Bonding	p. 27
Structure Factors	p. 27
Closed Packed Structures of Metals	p. 28
Alloys with Closed Packed Structure	p. 29
Hume-Rothery Rules for Formation of Solid Solutions	p. 30
Body Centered Cubic Structure	p. 33
Hume-Rothery Phases	p. 33
Ionic Structures	p. 35
Coordination Polyhedrons of Molecules	p. 38
The Band Model of Electrons in Solids	p. 41
Free electrons in a metal	p. 41
Orbitals in solids	p. 43
Density of states (DOS)	p. 46
Filling up with electrons; Fermi energy	p. 47
Crystal orbital overlap population: the formation of bonds	p. 48
Extension to more dimensions	p. 49
Band structure of d-metals	p. 52
Semiconductors: example TiO[subscript 2]	p. 53
Peierls distortion	p. 53
Energy bands in electrolytes	p. 55
Cohesion in Solids	p. 56
Lattice enthalpy	p. 56
Sublimation enthalpy	p. 57
Bond energies of metals	p. 57
Bond energies of alloys	p. 60
Electrode Potentials	p. 71
Pure Metals	p. 71
Equilibrium between a metal phase and an electrolyte phase	p. 71
Standard electrode potentials	p. 72
Standard electrode potentials of metal complexes	p. 79
Alloys	p. 80
Partial molar Gibbs energies	p. 80
Electrochemical measurements of partial molar functions	p. 83
Ag[subscript x]Au[subscript y]-example of a solid solution	p. 85
Partial molar functions of component B	p. 89
From partial molar functions to integral functions	p. 91
Intermetallic Phases and Compounds	p. 92
Potential versus mole fraction diagrams	p. 92
Coulometric titration	p. 94
Coulometric titration: the system LiAl	p. 94
Intermetallic compounds: the system LiSb	p. 97
Measurements at room temperatures: CuZn	p. 100
Ad-Atoms and Underpotential Deposition	p. 101
The Thermodynamic Description of the Interphase	p. 101
The electrochemical double layer	p. 101
Ideally polarizable electrodes	p. 105
Electrocapillary curves	p. 105
Adsorption isotherms	p. 107
Reversible electrodes	p. 109
Partial charge and electrosorption valency	p. 110
Thermodynamics of solid electrolyte interfaces	p. 113
Principal Methods for the Investigation of the Electrochemical Double Layer	p. 114
Measurement of capacitance	p. 114
Cyclic voltammetry and chronoamperometry	p. 118
Determination of the adsorbed mass	p. 119
Scanning tunneling microscopy and related methods	p. 122
Ad-Atoms	p. 126
Adsorption and desorption of ad-atoms	p. 127
Equilibrium ad-atom concentration	p. 128
Surface diffusion of ad-atoms	p. 129
Underpotential Deposition	p. 130
Lead on silver	p. 130
Copper on Au	p. 134
Underpotential deposition as two-dimensional phase formation	p. 137
Multiple steps of UPD film formation	p. 139
Mass Transport	p. 143
Stationary Diffusion	p. 143
Non-Stationary Diffusion	p. 147
Chronopotentiometry	p. 147
Chronoamperometry, chronocoulometry	p. 148
Warburg impedance	p. 150
Cyclic voltammetry	p. 154
Microelectrodes	p. 156
Diffusion in Solid Phases	p. 157
Potentiostatic method	p. 157
Galvanostatic method	p. 160
Methods to Control Diffusion Overpotential	p. 161
Rotating-disc electrode	p. 162
Rotating ring-disc electrodes	p. 165
Rotating-cylinder electrodes	p. 166
Charge Transfer	p. 169
Electron Transfer	p. 169
Butler-Volmer equation	p. 170
Tafel lines	p. 172
Charge transfer resistance	p. 174
Theories of electron transfer	p. 175
Electrochemical Reaction Orders	p. 178
Determination of electrochemical reaction orders from Tafel lines	p. 179
Determination of electrochemical reaction orders from the charge transfer resistance	p. 180
Ion Transfer	p. 184
Charge Transfer and Mass Transport	p. 186
Elimination of diffusion overpotential with a rotating disc electrode	p. 188
Elimination of diffusion contribution to the overpotential in chronoamperometry and chronopotentiometry	p. 190
Elimination of diffusion contributions to the overpotential by impedance spectroscopy	p. 193
Nucleation and Growth of Metals	p. 195
Nucleation	p. 195
Three-dimensional nucleation	p. 195
Two-dimensional nucleation	p. 197
Rate of nucleation	p. 198
Instantaneous and progressive nucleation	p. 200
Intermediate States of Electrodeposition	p. 203
Crystallization overpotential	p. 203
Surface Dynamics	p. 205
Residence time in kink site positions	p. 205
Calculation of the residence time	p. 207
Density of Kink Site Positions	p. 209
Equilibrium conditions	p. 209
Deposition conditions	p. 209
Experimental Investigations of Electrodeposition	p. 212
Electrodeposition on amalgam electrodes	p. 212
Investigations on solid electrodes	p. 212
Applications of electrodeposition from aqueous solvents	p. 215
Parallel reactions	p. 217
Deposition From Non-Aqueous Solvents	p. 217
Aluminum deposition from a molten salt	p. 217
Aluminum deposition from an organic electrolyte	p. 218
Aluminum deposition from ionic liquids	p. 219
Additives	p. 220
Adsorption, the hard-soft concept	p. 221
Influence of additives on deposition at different crystallographic faces	p. 222
Anodic stripping to study additive behavior	p. 223
Optical Spectroscopy to Study Metal Deposition	p. 223
Raman spectroscopy on silver in cyanide electrolytes	p. 224
Raman spectroscopy of organic additives	p. 226
Deposition of Alloys	p. 231
Deposition Potential and Equilibrium Potential	p. 231
Alloy Nucleation and Growth: The Partial Current Concept	p. 232
Brenner's Alloy Classification	p. 233
Mixed Potential Theory	p. 234
Surface Selectivity in Alloy Deposition	p. 235
Kink site positions of alloys	p. 235
Rate of separation and residence times	p. 236
Residence time and structure of alloys	p. 237
Markov Chain Theory; Definition of the Probability Matrix	p. 238
Equilibrium of the crystallization process	p. 238
Rate controlled processes	p. 240
Determination of selectivity constants	p. 241
Alloy characterization by selectivity constants	p. 242
Selectivity constants and residence times in kink site positions	p. 243
Experimental Examples	p. 243
The cobalt-iron alloy system	p. 243
Cobalt-nickel	p. 247
Iron-nickel	p. 249
Induced electrodeposition: the NiMo system	p. 251
Ternary Systems	p. 258
Kink site positions of ternary systems	p. 258
The Markov chain theory for ternary systems	p. 259
Example: prediction of the composition of CoFeNi alloys	p. 260
Oxides and Semiconductors	p. 263
Electrochemical Properties of a Semiconductor	p. 263
Band model of a semiconductor	p. 263
Semiconductor-electrolyte contact	p. 265
Gap states and surface states	p. 267
Current-potential curves	p. 267
Space-charge capacitance	p. 270
Photoelectrochemistry of Semiconductors	p. 271
Photocurrents	p. 271
Intensity modulated photocurrent spectroscopy (IMPS)	p. 275
Photopotentials and photopotential transients	p. 276
Spectroscopic Methods	p. 277
In situ spectroscopic methods	p. 277
In situ X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS)	p. 278
In situ Mossbauer spectroscopy	p. 280
Ex situ methods	p. 280
Microscopy	p. 280
Oxide Particles	p. 282
Batteries	p. 282
Lithium ion batteries	p. 283
TiO[subscript 2]-based photovoltaic cells	p. 284
Catalytic activity of oxide particles	p. 285
Oxide Layers	p. 286
Electrochemical Deposition of Semiconductors	p. 287
Corrosion and Corrosion Protection	p. 291
Corrosion	p. 291
Fundamental processes	p. 292
Mechanism of metal dissolution	p. 295
Mechanisms of compensation reactions	p. 297
Iron and steel	p. 298
Metallurgical aspects of iron and steel	p. 299
Copper	p. 300
Zinc	p. 301
Corrosion products	p. 301
Corrosion of alloys	p. 302
Corrosion Protection	p. 305
Passivity	p. 307
Cathodic protection	p. 316
Corrosion inhibition	p. 316
Phosphatizing	p. 318
Chromatizing	p. 319
Corrosion protection by surface coatings	p. 319
Intrinsically Conducting Polymers	p. 323
Chemical Synthesis	p. 325
Electrochemical Synthesis and Surface Film Formation	p. 326
Film Formation with Adhesion Promoters	p. 329
Ion Transport During Oxidation-Reduction	p. 330
Analyzing oxidation-reduction cycles using QCMB	p. 331
Electrical and Optical Film Properties	p. 335
Impedance of conducting polymers	p. 335
Neutral state properties	p. 338
Photoelectrochemical properties	p. 339
Polaron-bipolaron model of conducting polymers	p. 339
Spectro-electrochemical methods	p. 343
Copolymerization	p. 343
Mechanism of copolymerization	p. 345
Structure analysis of copolymers	p. 349
Properties of copolymers	p. 356
Corrosion Protection by Intrinsically Conducting Polymers	p. 356
Film formation on non-noble metals	p. 357
Kinetic experiments of corrosion protection	p. 357
Role of anions for a possible corrosion protection of conducting polymers	p. 359
Nanoelectrochemistry	p. 365
Going to Atomic Dimensions	p. 365
Co-Deposition	p. 365
Particle dispersions	p. 367
Determination of the zeta potential	p. 367
Factors influencing zeta potential and particle properties	p. 370
Properties of the metal surface	p. 371
Process parameters influencing the incorporation	p. 372
Mechanistic models	p. 372
General concepts for the development of a model	p. 378
Examples	p. 382
Compositionally Modulated Multi-Layers	p. 383
Plating of multi-layers	p. 383
Examples of multi-layers	p. 384
Core-Shell Composites	p. 384
Preparation procedure	p. 386
Particle characterization: applications	p. 387
Index	p. 389
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Electrochemistry for Materials Science

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Hardcover

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