كتاب Fundamental Aspects of Electrometallurgy

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Fundamental Aspects of Electrometallurgy
Konstantin I. Popov
University of Belgrade
Belgrade, Yugoslavia
Stojan S. Djokic
Westaim Corporation
Fort Saskatchewan, Alberta, Canada
Branimir N. Grgur
University of Belgrade
Belgrade, Yug

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CONTENTS
1. WHAT IS ELECTROMETALLURGY 1
1.1 Further Readings
2. DEFINITIONS, PRINCIPLES AND CONCEPTS
2.1 Basic Facts
2.1.1 Electrodes and electrochemical reactions, cell and circuit
2.1.2 The electrochemical double layer and possible
electrochemical reactions
2.2 Self Driving Cells
2.2.1 The Nernst equation and energy producing cells
2.2.2 Cementation
2.3 Electrolysis
2.3.1 Decomposition voltage
2.3.2 A cell with an insoluble anode
2.3.3 A cell with a soluble anode
2.3.4 Current efficiency
2.3.5 Faraday’s law
2.3.6 The current density—overpotential relationships
2.3.6.1 Basic equations
2.3.6.2 Some approximations
2.3.7 The cell voltage
2.4 Some Aspects of Electrocrystallization
3. SURFACE MORPHOLOGY OF METAL ELECTRODEPOSITS
2.5 Conclusions
2.6 Further Readings
Specific energy consumption
Thin Compact Surface Metal Films
Crystallization overpotential
3.1.2 The nucleation exclusion zones
Basic definitions
Physical simulation
Nucleation rate and deposition overpotential
Deposition from simple salt solutions
Deposition from complex salt solutions
Deposition in the presence of adsorbed additives
Inorganic compounds
Organic compounds
3.1.7 Conclusions
3.2 Thick Compact Metal Electrodeposits
3.2.1 Coarse surfaces
Mathematical models
Physical simulation
Real systems
3.2.1.3.1 Optimum current density for compact metal
deposition
Cauliflower like forms
Carrot like forms
3.2.2 Smooth surfaces
Basic facts
Model of leveling
Quantitative treatment
3.2.3 Bright surfaces
Silver mirror
Electropolished surfaces
Electrodeposited surfaces
Conclusions
3.3 Disperse Deposits
3.3.1 Spongy deposits
Mathematical model
Physical model
Real systems
3.3.2 Dendritic deposits
Mathematical model
Physical simulation
Real systems
Powdered deposits
Granular deposits
Whisker deposits
Conclusions
3.4 Further Readings
4. THE CURRENT DISTRIBUTION IN ELECTROCHEMICAL
CELLS
4.1 Two Equal Plane Parallel Electrodes Arrangement
Ohmic resistance of the cell
The very edge ohmic resistance
The edge effect
The depth of the penetration of a current line between
the electrode edges and the cell side walls
Mathematical model
Cell voltage-current density dependencies
Determination of the current density distribution
4.1.5 Quantitative treatment
4.1.5.1 Calculation of the cell voltage-current density
distribution dependences
4.1.5.2 The critical current density for dendritic growth
initiation at the edges
4.2 Cells with Low Anode Polarisation
4.2.1 The dependence of the current density at the tip of a
stationary wire electrode on the current density in the middle
of the electrode
4.2.2 Experimental evidence
The effect of ohmic resistance
Deposition in the presence of strongly adsorbed
organic additives (effect of increased cathodic Tafel
slope)
4.2.2.3 Deposition from a complex salt solution (effect of
exchange current density)
4.3 Corner Weakness Phenomena in Electroforming
Ohmic controlled deposition
Mixed activation - diffusion - ohmic controlled deposition
Activation - diffusion controlled deposition
Conclusions
Further Readings
5. ELECTRODEPOSITION AT A PERIODICALLY CHANGING
RATE
5.1 Basic Definitions
Reversing current
Pulsating current
Alternating current superimposed on direct current
5.1.4 Pulsating overpotential
5.2 Surface Concentration of Depositing Ions in the Periodic
Condition
5.2.1 Electrodeposition with periodically changing rate in the
millisecond range
Capacitance effects
Reversing current in the second range
5.3 Prevention of the Formation of Spongy Deposits and the Effect on
Dendritic Particles
5.4 Compact Deposits
Surface film
Electrode surface coarsening
Current Density and Morphology Distribution on a Macroprofile
Conclusions
Further Readings
6. ELECTROWINNING
Theoretical Aspects of Electrowinning
Theoretical Aspects of Zinc Electrowinning
6.2.1 Technological scheme of zinc electrowinning
6.3 Further Readings
7. ELECTROREFINING
7.1 Theoretical Aspects of Electrorefining
7.1.1 Selectivity of metal dissolution and deposition
7.2 Theoretical Aspect of Copper Electrorefining
7.2.1 Technological scheme of copper electrorefining
Refining of the electrolyte
Processing of the anodic slime
7.3 Further Readings
8. OPTIMUM CONDITIONS FOR ELECTROPLATING
Cementation and Deposition from the Complex Salt Solutions
The Porosity of Metal Electrodeposits
The Condition for the Deposition of a Coating with a Minimum
Porosity
8.4 Further Readings
9. ELECTROPLATING AND SURFACE FINISHING
Electrodeposition of Alloys
Electrodeposition of Composite Materials
Electroforming
Electroplating from Non-Aqueous Electrolytes
Electroplating from Room Temperature Molten Salts
Electropolishing
Electromachining
Electrochemical Oxidation of Metals
Further Readings
10. METAL DEPOSITION WITHOUT AN EXTERNAL
CURRENT
10.1 Basic Definitions
Displacement deposition
Contact deposition
Autocatalytic deposition
Solutions for Electroless Deposition
Mechanistic Aspects of Electroless Deposition
The atomic hydrogen mechanism
The hydride ion mechanism
The electrochemical mechanism
Metal hydroxide mechanism
The universal mechanism
10.4 Applications and Properties of Electroless Deposited Films
Metallization of non-conductive surfaces
Electroless deposition of composite coatings
Electroless deposition of gold
Electroless deposition of other metals
10.5 Further Readings
11. ELECTRODEPOSITION OF METALS FROM MOLTEN SALTS
Ionically Conducting Melts
Electrochemical Studies in Electrodeposition from Molten Salts
11.2.1 Electrolysis of alumina-cryolite melts
The Anode Effect
Nonconsumable Anode Materials in Molten Salts
Electrodeposition
11.5 Further Readings xviii Contents
12. ENVIRONMENTAL ISSUES
12.1 Environmental Concerns in the Electrowinning and Electrorefining
from Aqueous Solutions
Environmental Concerns in the Molten Salts Electrolysis
Environmental Concerns in the Electroplating Technologies
Further Readings
INDEX

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