Treatise on Process Metallurgy

Cover Page
Title Page
Copyright
Dedication
Preface
Editor in Chief
Contributors to volume 1
Acknowledgement
	The Review Committee
Process Metallurgy?An Argosy Through Time
	Introduction
	Alchemy and the Discovery of Metals
	Development of Extraction Processes
	References
Introduction to Metallurgical Processing
	Recent Development Trends
		Drivers for Change
		Process Trends
	Process Options
		Process Stages and Aims
		Alternative Process Routes
		Alternative Process Routes for Selected Metals
	Classification of Metallurgical Reactors
		Gas/Solid Reactors
			Shaft Furnaces
			Rotary Kiln
			Fluidized Beds
			Entrained Flow Reactors
			Moving and Fixed Grate Reactors
		Liquid/Solid Reactors
			In Situ Leaching
			Heap Leaching
			Percolation Leaching
			Agitation Leaching
			Crystallizers/Precipitation Reactors
			Electrochemical Production Reactors
			Ion Exchange Reactors
		Liquid-Phase Reactors
			Gas/Liquid Reactors
				Bath Smelting Processes
				Bath Refining Processes
			Liquid/Liquid Reactions
		Multistep Reactors
			Blast Furnaces and Other Counter Current Reactors
			Reverberatory Furnaces
			Flash Smelting Processes
			Multistage Smelting Processes
			Solvent Extraction
	Summary of General Characteristics of Metallurgical Reactors
		Pyrometallurgy
		Hydro- and Electrometallurgical Reactors
	Reactor and Process Design Methodologies
	Summary
	Reference
Structure and Properties of Matter
	State and Equilibrium
	State of Matter
	Solid
	Liquid
	Gas
	Glass=Amorphous Solid
	Plasma
	Phase Transition
	Glass Transition
	Description of Structural Features of Liquid
	Structural Features of Metallic and Oxide Melts
	References
Structure and Properties of Molten Metals
	Structure
		Introduction
		Levitation Methods
		X-ray and Neutron Diffraction?Basics
		Results
			Pure Elements
			Alloys
	Properties
		Experimental Techniques
			Pyrometry
			Thermal Expansion and Density
				Maximum Bubble Pressure
				Dilatometers
				Capillary Dilatometers
				Push-rod Technique
				Levitated Drop
			Thermal Properties
				Differential Scanning Calorimetry
				Drop Calorimetry
				Modulation Calorimetry
			Thermal Conductivity and Thermal Diffusivity
			Electrical Conductivity
			Mass diffusion
			Surface Tension
				Maximum Bubble Pressure
				Sessile Drop
				Oscillating Drop
			Viscosity
				Capillary Viscometer
				Rotating Cup Viscometer
				Oscillating Cup Viscometer
				Oscillating Drop
		Results
			Pure Metals
				Emissivity
				Density and Thermal Expansion
				Specific Heat
				Thermal Conductivity
				Electrical Resistivity
				Self-diffusion
				Viscosity
				Surface Tension
			Alloys
	Structure-Property Relations and Interproperty Relations
		Structure-Property Relations
		Interproperty Relations
	Summary
	References
The Structure and Properties of Silicate Slags
	Introduction
	Structure of Slags and Glasses
		Structure of Silicates
		Structure of Aluminosilicates
		The Effect of Fe2O3 and Cr2O3 on Silicate Structure
		Effect of TiO2 and ZrO2 on Silicate Structure
		Effect of CaF2 and B2O3 on Silicate Structure
		Parameters to Represent the Structure of Slags
			Basicity
			NBO/T and Q
			Optical Basicity 㼀
			Concentrations of O0, O-, and O2-
			Qn Values
			Viscosity
		Effect of Cations on Structure
		Structural Characteristics
			Nature of Structural Units
			Coordination Number of Cations Ncoord
			Topology, Bond Angles, Bond Energies
			Configurational Entropy
		Structural Information
			Silicates
			Aluminosilicates
			Titano-Silicates
			Silicates Containing Iron Oxides
			Additions of CaF2
		Methods of Determining Structure
			X-ray, Electron, and Neutron Diffraction
			Infrared, Ultraviolet, and Raman Spectroscopy
			NMR Spectroscopy
			Electron Spin Resonance
			Mossbauer Spectroscopy
			X-ray Absorption Spectroscopy XANES and EXAFS
			X-ray Emission Spectroscopy
			X-ray Photon Spectroscopy or ESCA
	Effect of Structure on Properties
		Effect of Silicate Structure on Properties of Slags
			Silicates
			Aluminosilicates
		Effect of Cations on Slag Properties
			Strength of the Ionic M+-O- Bond
			Fraction of Ionic Bonding in the MO Bond
			Size of the Cations
			The Bridging of Cations
			The Number of Cations
			Mixed Alkali Effect
		Effect of Temperature on Properties
			Solid Slags
			Liquid Slags
	Properties of Slags Based on Silicate Network
		Thermodynamic Properties
			Liquidus Temperature Tliq
				The Importance of Tliq in Industrial Processes
				Factors Affecting Tliq
				Measurement Methods
				Tliq Data for Slags
				Calculation of Tliq
			Activity Coefficients and other Thermodynamic Properties
				Why Thermodynamic Property Data are Needed
				Factors Affecting Activities and Other Thermodynamic Functions
			Heat Capacity Cp HT-H298, Entropy, Entropy of Fusion DeltaSfus
				Factors Affecting Cp and Enthalpy
				Measurement Methods
	Acknowledgments
	References
Introduction
Atomistic Computer Simulation Techniques
	MC Method
		Basic Approach
		Statistical Ensembles
			Micro-Canonical Ensemble for Isolated Systems
			Canonical Ensemble for Closed Systems
			Grand Canonical Ensemble for Open Systems
			Isobaric Isothermic Ensemble
		Sampling Procedures
		Trial Moves and Boundary Conditions
		Random Numbers and Accuracy Considerations
	MD Method
		Basic Approach
		Ensembles
			Constant Temperature Ensemble
			Constant Pressure Ensemble
		Accuracy Considerations
	Ab initio Density Functional Theory
		Basic Approach
		Applications to Materials Science
		Current Limitations and Future Directions
Special Techniques and Advanced Algorithms
	Kinetic Monte Carlo Method
	Reverse Monte Carlo Method
	Hybrid MC Methods
	The Gibbs Ensemble Method
	Biased MC Schemes
	Wang?Landau Formalism
	Parallel Tempering Method
Determination of Physical Properties
	Free Energy
	Surface Tension
	Wettability
	Phase Diagrams and Critical Phenomena
	Diffusion
Atomistic Interaction Potentials
	Fundamentals
		Beyond Pair Potentials
		Development of Interatomic Potentials/Parameters
	Interaction Potentials for Iron
		Finnis?Sinclair Potential
		Embedded-Atom Method
		Analytic Bond-Order Potential
		Models for Simulations on Liquid iron in the Earth's Outer Core: Sutton?Chen Potentials
	Interaction Potentials for Other Metals
		Finnis?Sinclair Potentials for Transition Metals
		Modified Embedded-Atom Method Potentials for Cubic Materials and Impurities
		EAM Potentials for Liquid Transition Metals
		Sutton?Chen Potentials
		Interatomic Potentials from First-Principles Calculations
	Interaction Potentials for Covalently Bonded Group IV Elements
		Silicon
			Stillinger and Weber Potential
			Tersoff Potential
			Other Potentials
		Carbon
			Tersoff Potential
			Brenner Potential
			Nonbonded Macro-Molecular Potentials
	Interaction Potentials/Parameters for Binary and Ternary Systems
		Fe?C System
			Interaction Potentials
References
Thermodynamic Aspects of Process Metallurgy: Introduction to Thermodynamics of Metallurgical
Processes
First, Second, and Third Laws of Thermochemistry
	Thermodynamic Data Compilations
	Ideal Gas
	The First Law of Thermodynamics
	Enthalpy and Heat Capacity
		Enthalpy
		Heat Capacity
		Temperature Dependence of Heat Capacity
		Temperature Dependence of Enthalpy
	The Second and Third Laws of Thermodynamics and Entropy
	Gibbs Energy
	Combined Statement of the First and Second Laws of Thermodynamics
	Changes in Gibbs Energy, Enthalpy, and Entropy Due to Reaction
	Gibbs Energy Function
	Appendix
	References
Phase Rule
	Intensive and Extensive Properties
	Degree of Freedom
	Phase
	System
	Condensed Phase-Vapor Equilibrium
	Arbitrary Choice of System
	Clapeyron Equation?Liquid Vapor Equilibrium
	Temperature Dependence of Vapor Pressure
	Solid?Liquid Equilibrium
	Triple Point
	Arbitrary Choice of System?Ionic Species
	Critical Temperature and Pressure
	Freedom Degree and Thermochemical Data?1
	Freedom Degree and Thermochemical Data?2
	Single-Phase Composition and Bulk Composition
	Composition of Industrial Slag
	References
Ellingham Diagram
	Standard Gibbs Energy Change of Formation of Compounds
	Equilibrium Oxygen Partial Pressure
	Equilibrium CO/CO2 Ratio and the Boudouard Reaction
	Influence of Activity of Condensed Phases on Gibbs Energy Change
	References
Solution Thermochemistry
	Partial Molar Quantities
	Integral Molar Quantities
	Relationship Between Partial Molar Quantities and Integral Molar Quantities
	Relative Partial Molar Quantities and Integral Molar Quantities
	Raoults Law and Ideal Solutions
	Excess Thermodynamic Quantities
	Integration of the Gibbs-Duhem Equation
	Regular Solutions
	Darkens Quadratic Formalism
	References
Thermodynamic Basis for Phase Diagrams
	Gibbs Energy of Binary Solutions
	Binary Isomorphous System
	Binary Eutectic System
	Binary Monotectic and Peritectic Systems
	Binary System Including an Intermediate Compound
	Consistency of Phase Diagram and Thermochemical Data of the Binary System CaO?SiO2
	Ternary Phase Diagram
	References
Dilute Solutions
	Henry's Law and Sieverts Law
	Henrian Activities and the Conversion of Standard States
	Description of Activities of Minor Solute Elements in Metallic Solution Wagner's Equation
	Examples for the Calculation of Henrian Activities
	Data Compilations for Dilute Liquid Alloys
		The Thermodynamics of Liquid Iron Alloys
		The Thermodynamics of Liquid Copper Alloys
		The Thermodynamics of Liquid Cobalt Alloys
		The Thermodynamics of Liquid Nickel Alloys
	References
Thermodynamics of Slags
	Phase Diagrams and Activities
	Basicity and Refining Ability of Slags
		Basicity of the Slags
		Optical Basicity
		Theoretical Optical Basicity
		Capacity and Dissolution
			Sulfide, Phosphate, and Carbonate Capacities [16]
			Phosphide and Nitride Capacities
			Other Capacities
	Structure and Thermochemical Models for Slags
		Temkin's and Flood et al.s Description of Ionic Melts [38]
		Richardson's Theory of Ideal Mixing of Silicates [38]
		Lumsden's Description of Silicates [38,43]
		Slag Models [38]
	Oxidation?Reduction Equilibrium in Slags
	References
Examples of Steelmaking Thermochemistry
	Fundamental Considerations Pertaining to Removal of Impurities from Molten Steel
	Effect of Solute Elements on Silicon Deoxidation of Ferrous Alloys
	Thermodynamics of Calcium Treatment of Al-Killed Steel
	Equilibrium Between Solid Oxides and Highly Alloyed Steels
	Thermodynamics of Calcium Treatment of Molten Iron
	Chemical Potential Control by Gas Equilibria
		CO+CO2+SO2+Ar Gas Mixture
		H2+CO2 Gas Mixture
	References
Thermodynamics of Aqueous Phases
	Chemical Potentials and Electrochemical Potentials
	Activity and Activity Coefficients
	Mean Activity Coefficients
	The Debye?Hückel Law [2]
	Chemical Equilibrium and Gibbs Energy of Formation of Ions
	Chemical Equilibrium in Aqueous Solutions
		Acid?Base Reaction
		Redox Reactions
	Potential?pH Diagrams Pourbaix Diagrams [6]
	References
Thermodynamic Basis of Electrolysis and Electrochemistry
	Zinc Electrowinning
	Copper Electrowinning
	Copper Electrorefining
	Electrochemistry in Leaching
	Oxidation
	Acidification
	Reduction
	References
Rate Phenomena in Process Metallurgy
	Introduction
		Importance of Transport Phenomena in Metallurgical Processing
		Basic Methodologies in Transport Phenomena
	Momentum Transfer
	Flow Description
		Steady and Unsteady Flows
		Uniform and Nonuniform Flows
		Streak Lines, Particle Paths, and Stream Lines
		Eulerian and Lagrangian Points of View
		Laminar and Turbulent Flows
		Incompressible and Compressible Flows
	Overall Energy Balance
	The Concept of Viscosity
	Steady-State Fully Developed Laminar Flow Through a Straight Pipe
	Buckingham Pi Theorem and Its Application to Transport Phenomena
	Reynolds Number
	Friction Factor for Flow Through Pipes
		Friction Losses from Pipe Fittings
		Estimation of Friction Factor for Flow Through Conduits Having Noncircular Cross Section
	Flow Through Packed Beds
	Fluidized Beds
		Minimum Fluidization Velocity, vmf
		Voidage in Particulate Fluidized Bed
		Voidage in Bubbling Fluidized Bed [21]
	Flow Around Particles
	Compressible Flow
		Compressible Flow Through a Pipe of Constant Cross Section
		Compressible Flow Through Convergent-Divergent de Laval Nozzle
	Momentum Balance at Differential Scale
		Equation of Continuity
		Navier-Stokes Equation
	Models of Turbulence
		Generic Flow Features in Turbulent Flows
		RANS Models
			Mixing-Length Theory
			κ- Model [29]
		LES Models
	Introduction to Heat Transfer
	Conservation Equation as Applied to Thermal Systems
	Conduction
		Conduction Equation
		Boundary Conditions
			Prescribed Surface Temperature
			Prescribed Heat Flux
			Convective Boundary Condition
			A Boundary Between Two Conducting Media
		1D Steady-State Conduction
			Conduction Through a Plane Wall
			Conduction Through Radial Systems
			Heat Transfer Through Extended Surfaces
		1D Transient Conduction
			Thermally Thin Bodies
			Thermally Thick Bodies
			Conduction in 1D
			Slab
			Long Cylinder and Sphere
			Semi-infinite System
	Convection
		Boundary Layer Theory
		Forced Convection: Heat Transfer Coefficient Correlations
		External Flow
			Flow over a Flat Plate
			Flow Across Cylinder
	References
Reaction Kinetics
	Reaction Kinetics and Reaction Systems
		Homogeneous Reactions
		Heterogeneous Reactions
	Reaction Rates and Rate-Limiting Processes
		Case a: Mass Transfer in Phase I is Rate Limiting
		Case b: Mass Transfer in Phase II is Rate Limiting
		Case c: Mass Transfer in Both Phases I and II are Rate Limiting
		Case d: Chemical Reaction at the Interface is Rate Limiting
		Case e: Overall Rate Equation
	Structure of the Chapter
	References
Chemical Reaction Kinetics
	Chemical Kinetics
		Empirical Rate Equations
		Reaction Rate Theory
		Reactions at Interfaces
	Electrochemical Reactions
		Rate Equations
		Electrochemical Cells
		Half-Cell Reactions
		Coupled Reactions
	Reversible Processes
	References
Chemical Reactions at Moving Surfaces: Shape Change, No Phase Change
	Reaction Rates on Fluid/Condensed Phases Interfaces
		Reactions with the Gas Phase
		Thermodynamic Driving Force for the Reaction
		Removal of Species from Solid Surfaces
	Chemical Reactions on Moving Solid Surfaces
		Chemical Reaction Rates on Moving Surfaces
		The Influence of Atomic Roughness on Chemical Reactions Rates
	Reactions with Accumulation at the Interface
		Conditions for Instability Formation at Moving Interfaces
		Oxide Surface Morphologies in Reactive Gas Atmospheres
	Summary
	References
Phase Formation Reactions
	Classes of Phase Formation Reactions
	Elementary Reaction Processes
		Continuum Phase Formation Reactions Spinoidal
		Heterogeneous Phase Formation Reactions Nucleation and Growth
			Nucleation
	Mechanisms of Growth
		Introduction
		Rates of Reconstructive Transformations
			Growth of New Phases
	Summary
	References
Chemical Kinetics+Phase Changes+Shape Changes
	Introduction
		Chemical Reactions on Metal Surfaces
	Metal Growth Morphologies
		Dendritic Pore Formation
		Metal Whisker Growth
		Continuous and Discontinuous Metal Layer Growth
		Coupled Growth
		Analogies with Solid/Liquid and Solid/Solid Systems
	Morphology Maps
	Summary
	References
Factors Influencing Reaction Area
	Introduction
	Reactant Characteristics
		Fluid/Fluid Systems
			Composition
			Bulk Flow
		Fluid/Solid Systems
			Particle Characteristics
	Reaction Induced Phenomena
		Fluid/Fluid Systems
			Emulsification
			Gas Phase Formation
		Fluid/Solid Systems
			Product Structure
			Reaction Micromodels for Nonplanar Interfaces
	Reaction Time/Extent
		Fluid/Fluid Systems
		Fluid/Solid Systems
	Summary
	References
Reaction System Performance
	Driving Forces for Reaction
	Reaction Engineering and Process Models
		Batch/Semibatch Discontinuous Reactors
		Continuous Flow Reactors
		Complex Reactor Models
	Summary
	References
Index
	A
	B
	C
	D
	E
	F
	G
	H
	I
	J
	K
	L
	M
	N
	O
	P
	Q
	R
	S
	T
	U
	V
	W
	X
	Z