II Thermochemical

Materials Science
Fall, 2008
PART II: THERMOCHEMICAL PROPERTIES
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CHAPTER 7: THERMODYNAMICS
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7.1
Introduction
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7.2 Entropy
7.2.1 Entropy and time
7.2.2 Entropy and heat
7.2.3 Entropy and randomness
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7.3 The Conditions of Equilibrium

7.3.1 The equilibrium of an isolated system
7.3.2 Internal equilibrium
7.3.3 Non-equilibrium states; constrained equilibria
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7.4 The Thermodynamic Potentials

7.4.1 The Helmholtz free energy
7.4.2 The Gibbs free energy
7.4.3 The work function
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7.5 The Fundamental Equation

7.5.1 The entropy function
7.5.2 The energy function
7.5.3 Alternate forms of the fundamental equation
7.5.4 The integrated form of the fundamental equation
7.5.5 The statistical form of the fundamental equation
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7.6 The Thermodynamics of Surfaces

7.6.1 The Gibbs construction
7.6.2 The fundamental equation of an interface
7.6.3 The conditions of equilibrium at an interface
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CHAPTER 8: SIMPLE SOLIDS

8.1
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Introduction
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8.2 The Perfect Crystal

8.2.1 The internal energy
8.2.2 Lattice vibrations
8.2.3 The vibrational energy
8.2.4 The vibrational contribution to the specific heat
8.2.5 A qualitative version of the Debye model
8.2.6 The electronic contribution to the specific heat
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8.2.8 Thermodynamic properties
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8.3 The Random Solid Solution

8.3.1 The Bragg-Williams model
8.3.3 The configurational entropy
8.3.4 The free energy and thermodynamic behavior
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8.4 Equilibrium Defect Concentrations

8.4.1 The equilibrium vacancy concentration
8.4.2 Dislocations and grain boundaries
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CHAPTER 9: PHASES AND PHASE EQUILIBRIUM

9.1
Introduction
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9.2 Phase Equilibria in a One-Component System

9.2.1 Phase equilibria and equilibrium phase transformations
9.2.2 Metastability
9.2.3 First-order phase transitions: latent heat
9.2.4 Transformation from a metastable state
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9.3 Mutations
9.3.1 The Nature of a Mutation
9.3.2 Common Transitions that are mutations
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9.4 Phase Equilibria in Two-Component Systems

9.4.1 The free energy function
9.4.2 The common tangent rule
9.4.3 The phases present at given T, P
9.4.4 Equilibrium at a congruent point
9.4.5 Equilibrium at the critical point of a miscibility gap
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9.5
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Binary Phase Diagrams
9.6 The Solid Solution Diagram

9.6.1 The thermodynamics of the solid solution diagram
9.6.2 Equilibrium information contained in the phase diagram
9.6.3 Equilibrium phase changes
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9.7 The Eutectic Phase Diagram

9.7.1 Thermodynamics of the eutectic phase diagram
9.7.3 Precipitation from the phase
9.7.4 The eutectic microstructure
9.7.5 Mixed microstructures in a eutectic system
9.7.6 Phase diagrams that include a eutectoid reaction
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9.8 Common Binary Phase Diagrams

9.8.1 Solid solution diagrams
9.8.2 Low-temperature behavior of a solid solution
9.8.3 Phase diagrams with eutectic or peritectic reactions
9.8.4 Structural transformations in the solid state
9.8.5 Systems that form compounds
9.8.6 Mutation lines in binary phase diagrams
9.8.7 Miscibility gap in the liquid
CHAPTER 10: KINETICS
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10.1 Introduction
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10.2 Local Equilibrium
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10.3 The Conduction of Heat

10.3.1 Heat conduction in one dimension: Fourier's Law
10.3.2 Heat conduction in three dimensions
10.3.3 Heat sources
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10.4 Mechanisms of Heat Conduction

10.4.1 Heat conduction by a gas of colliding particles
10.4.2 Heat conduction by mobile electrons
10.4.3 Heat conduction by phonons
10.4.4 Heat conduction by photons
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10.5 Non-equilibrium Thermodynamics

10.5.1 The thermodynamic forces
10.5.2 The non-equilibrium fluxes and the kinetic equations
10.5.3 Simplification of the kinetic equations
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10.6 Diffusion
10.6.1 Fick's First Law for the diffusion flux
10.6.2 Fick's Second Law for the composition change
10.6.3 Solutions of the diffusion equation
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10.7 The Mechanism of Diffusion in the Solid State

10.7.1 The mobility of interstitial species
10.7.2 The mobility of substitutional species
10.7.3 Random-walk diffusion; Fick's First Law
10.7.4 The mean diffusion distance in random walk diffusion
10.7.5 Uses of the mean diffusion distance
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10.8 Microstructural Effects in Diffusion

10.8.1 The vacancy concentration
10.8.2 Grain boundary diffusion
10.8.3 Diffusion through dislocation cores
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CHAPTER 11: PHASE TRANSFORMATIONS
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11.1 Common Types of Phase Transformations
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11.2 The Basic Transformation Mechanisms

11.2.1 Nucleated transformations and instabilities
11.2.2 First-order transitions and mutations
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11.3 Homogeneous Nucleation

11.3.1 Nucleation as a thermally activated process
11.3.2 The activation energy for homogeneous nucleation
11.3.3 The nucleation rate
11.3.4 The initiation time
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11.4 Heterogeneous Transformations

11.4.1 Nucleation at a grain boundary
11.4.2 Other heterogeneous nucleation sites
11.4.3 Implications for materials processing
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11.5 The Thermodynamics of Nucleation

11.5.1 The thermodynamic driving force for nucleation
11.5.2 Nucleation in a one-component system
11.5.3 Nucleation from a supersaturated solid solution
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11.6 Nucleation of Non-Equilibrium States

11.6.1 Congruent nucleation
11.6.2 Coherent nuclei
11.6.3 Nucleation of metastable phases: the Ostwald rule
11.6.4 Sequential Nucleation in a Eutectic
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11.7 Recrystallization
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11.8 Growth
11.8.1 Primary growth and coarsening
11.8.2 Time-temperature-transformation (TTT) curves
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11.9 Interface-Controlled Growth

11.9.1 Isotropic growth of a congruent phase
11.9.2 Interface control at stable surfaces
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11.10 Diffusion-Controlled Growth

11.10.1 Growth controlled by thermal diffusion
11.10.2 Growth controlled by chemical diffusion
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11.11 Chemical Segregation During Growth
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11.12 Grain Growth and Coarsening
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11.13 Instabilities
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11.14 Martensitic Transformations
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11.15 Spinodal Decomposition

11.15.1 Spinodal instability within a miscibility gap
11.15.2 Spinodal decomposition
11.15.3 Spinodal decomposition to a metastable phase
11.15.4 Use of spinodal decomposition in materials processing
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11.16 Ordering Reactions

11.16.1 Ordering reactions that are mutations
11.16.2 First-order transitions that change the state of order
11.16.3 Ordering at the stoichiometric composition
11.16.4 Ordering at an off-stoichiometric composition
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CHAPTER 12: ENVIRONMENTAL INTERACTIONS
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12.1 Introduction
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12.2 Chemical Changes near the Surface

12.2.1 Thermal treatment
12.2.2 Diffusion Across the interface
12.2.3 Ion implantation
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12.3 Chemical Reactions at the Surface: Oxidation

12.3.1 Thermodynamics of oxidation
12.3.2 The kinetics of oxidation
12.3.3 Protecting against oxidation
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12.4 Electrochemical Reactions

12.4.1 The galvanic cell
12.4.2 The electromotive series and the galvanic series
12.4.3 The influence of concentration: concentration cells
12.4.4 Reactions at the cathode
12.4.5 The influence of an impressed voltage
12.4.6 Thermodynamics of the galvanic cell
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12.5 The Kinetics of Electrochemical Reactions

12.5.1 The current in an electrochemical cell
12.5.2 The current-voltage characteristic
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12.6 Aqueous Corrosion in Engineering Systems

12.6.1 Corrosion cells in engineering systems
12.6.2 The corrosion rate
12.6.3 Corrosion protection
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Part II: Thermochemical Properties

...In war the victorious strategist seeks battle after the victory has been
won, while he who is destined for defeat fights first and looks for victory
afterwards
- Sun Tzu, The Art of War
The thermochemical properties of materials govern two kinds of behavior:

internal reactions that occur within the material and determine its microstructure, and
environmental interactions that alter the chemistry of the material or its environment.
The most important of these are the reactions that are manipulated to control
microstructure and fix engineering properties. The management of thermochemical
processes within the material is the essence of materials processing. Thermochemical
properties also affect behavior in service. If the microstructure evolves as a material is
used its engineering properties change accordingly. Such changes must be anticipated
and, if necessary, prevented.
To understand thermochemical processes it is necessary to recognize the interplay
of two central themes: thermodynamics and kinetics. Thermodynamics governs whether
a given process is possible and fixes the magnitude of the forces that drive it. Kinetics
determines how quickly the process can happen, given the thermodynamic driving force.
In many cases, kinetic constraints are used to prevent thermodynamically favorable
processes from happening at all. Virtually all useful materials have microstructures that
would spontaneously change if they were free to do so. They are, nonetheless, useful
because the rate of change is negligible. Silica glasses and amorphous polymers are used
routinely despite the fact that the crystalline state is preferred, and crystallization will
eventually occur. Almost all metallic structures are polygranular despite the fact that
grain boundaries are unfavorable, high-energy defects that will eventually be removed by
grain growth. Electronic devices employ silicon chips that are doped to create chemical
heterogeneities that will eventually homogenize and disappear. These are all examples of
useful microstructures that are maintained by kinetic constraints. Because the kinetics of
change are slow, "eventually" is a time much longer than the expected life of the device
in which the engineer uses it (and, often, much longer than the expected life of the
engineer).
Materials are made to have useful microstructures by combining thermodynamics
and kinetics in a constructive way. The material is brought into a condition in which the
microstructure that is wanted is both thermodynamically possible and kinetically achievable. The conditions are then altered, usually by cooling, to prevent further microstructural changes. For example, glasses are manufactured by melting, then cooling
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quickly to a temperature at which both the amorphous and the crystalline solid states are
thermodynamically preferred to the liquid. Since the amorphous structure is easier to
achieve, it forms first. If the composition is such that crystallization is difficult and the
glass is kept reasonably cool, it will remain amorphous for as long as desired.
Chemically heterogeneous silicon chips are manufactured by allowing chemical species
to diffuse into particular regions of the silicon crystal at high temperature, then cooling to
a temperature at which the rate of subsequent diffusion is negligible. Almost all other
useful engineering materials are made in a conceptually similar way.
To appreciate how this is done it is necessary to understand both thermodynamics
and kinetics. In the following chapter we discuss thermodynamics. Thermodynamics defines the conditions of equilibrium, which lead to the notions of homogeneous phases,
which are volumes of material that have uniform structure and composition, and equilibrium phase diagrams, which are maps that show the phases that are preferred in a material
as a function of its temperature and composition. These concepts identify the two ways
in which the microstructures of materials evolve: heterogeneities in single-phase regions
diminish and vanish with time, and distinct phases appear or disappear as suggested by
the phase diagram. The rate at which these processes occur is governed by the kinetics of
diffusion in the former case, and the kinetics of structural change in the latter. The
kinetics of thermochemical changes will be treated in general, and then specifically
applied to the problems of chemical diffusion and structural change in the solid state.
The environmental interactions we shall specifically consider are those that
govern the deterioration of materials at high temperature or in aqueous environments:
high-temperature oxidation and aqueous corrosion. Both are important problems that
concern almost all branches of engineering.
Finally, we shall consider two types of catalytic behavior: wetting, in which a
solid determines the morphology of a second phase that may coat it, and chemical
catalysis, in which a solid promotes a chemical reaction in which it does not directly
participate. Wetting phenomena are important in coating, bonding and the catalysis of
structural change. Chemical catalysis is particularly relevant to chemical engineering,
and has given rise to a particular branch of materials science, the science of catalytic
materials.
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Chapter 7: Thermodynamics
The great German physicist, Boltzmann, spent a lifetime
deciphering the laws of thermodynamics, and died by his own hand. His
intellectual successor, Paul Ehrenfest, also killed himself. We shall now
study thermodynamics ...
- I can't recall who wrote this. However, per Oscar Wilde ,
a good quote should not be held responsible for its source.
7.1 INTRODUCTION
While the origins of materials engineering are lost in the mists of prehistory, it is
arguably possible to date the beginning of materials science. The year was 1876, and the
occasion was the publication of a paper by a then obscure Professor of Mathematical
Physics at Yale University named Josiah Willard Gibbs. The paper appeared in an even
more obscure scientific journal, the Transactions of the Connecticut Academy. It was
entitled "On the Equilibrium of Heterogeneous Substances", and it was the first part of a
two-part paper (the second part appeared in the same journal in 1878) that discussed how
the recently formulated laws of thermodynamics might be used to understand the
microstructures of materials.
For centuries before Gibbs, perceptive engineers had recognized that the
properties of materials were determined by their nature, or, as we would say today, by
their composition and microstructure. They also recognized that the nature of a material
could be intentionally modified or controlled by processing it in an appropriate way.
Even in the ancient world engineers achieved a degree of control over the materials they
used that is impressive today. But the rules that governed processing were almost
entirely empirical. The competent materials engineer was an artisan who resembled a
master chef more than a modern technologist. Recipes were passed from master to
apprentice, to be memorized rather than understood. Progress almost invariably reflected
accidental discovery or observations derived from casual experimentation.
The development of the thermodynamics of materials in the hands of Gibbs and
his successors revolutionized materials engineering and turned it into materials science.
The keys lay in Gibbs derivation of the fundamental equation that governs the properties
of a material, his demonstration that the fundamental equation could be written in
alternative forms to define convenient thermodynamic potentials that rule behavior in
common experimental situations, and his formulation of the conditions of equilibrium
and stability that determine when microstructural changes can occur. Much of this
information can be presented in the form of equilibrium phase diagrams that are plots of
the equilibrium states of materials under given conditions. The equilibrium phase
diagrams identify the state a material will seek under a given set of conditions, for
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example, a given composition, temperature and pressure, and can be used to infer the
microstructural changes that will happen when these conditions are altered.
Thermodynamics is a field in its own right that is the subject of a number of
courses in various disciplines. I assume that you have some familiarity with it from your
general background in chemistry and physics, and will give only a short overview here.
The content of thermodynamics that is essential to understand the thermochemical
behavior of materials includes the fundamental equation and the conditions of
equilibrium. Both of these are consequences of the Second Law of Thermodynamics,
which defines the entropy of a system. I shall assume that you are generally familiar with
the concept of energy and its conservation, which is the content of the First Law of
Thermodynamics, and move immediately to the Second Law.
7.2 ENTROPY
The concept of entropy is one of the most fundamental in science, and is also one
of the more difficult for the typical student to grasp. A major reason is that entropy is not
a thing that is easily seen or measured, and hence does not call up a concrete physical
picture of the type that often helps illustrate other fundamental principles of physics. To
understand entropy it is useful to think of it in connection with one of the more familiar
concepts with which it is intimately associated: time, heat, equilibrium, and probability.
7.2.1 Entropy and time
The classical definition of entropy likens it to time, in the sense of real, or evolutionary time. To illustrate how and why we consider the simple system shown in Fig.
7.1. The system contains a uniform gas in a container whose walls insulate it from
thermal or chemical interaction with its environment. Such a container is called
adiabatic, and establishes a situation in which the state of the gas within the container can
only be changed by doing mechanical work on it. In the example shown mechanical
work can be done by displacing the piston at one end of the container or by rotating the
paddle-wheel in its interior. The state of the gas is defined by its fixed chemical
composition ({N}, the set of atom or mole numbers of the components it contains), by its
volume (V), which can be changed by displacing the piston, and by its internal energy
(E), which can be changed in the positive sense by compressing the piston or turning the
paddle wheel to do mechanical work on the system, and in the negative sense by
displacing the piston to expand the gas so that it does work on its environment.
It is found experimentally that all of the possible states of a gas in an adiabatic
container can be divided into three sets on the basis of their accessibility from the initial
state. The first set (1) includes states that can be reached in a reversible way from the
initial state. These states are achieved by displacing the piston so slowly and smoothly
that friction and turbulence are negligible. The initial state can be recovered by slowly
returning the piston to its original position. The second set (2) includes all other states
that can be reached from the initial state without changing the nature of the system or its
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adiabatic container. The transitions that lead to these states are irreversible: the system
can never return to its original state as long as it remains adiabatic. All states that are
reached by processes that stir the gas by turning the paddle wheel fall into this category.
One can introduce an arbitrary amount of energy into the gas by turning the paddle
wheel, but once this is done and the gas has become quiescent the wheel will never
spontaneously turn itself to do work on the environment. The third set (3) includes all
states that are inaccessible in the sense that they cannot be obtained from the initial state
by any adiabatic process at all. These states have the property that they could only be
reached if the energy could be decreased at constant volume, but this could only happen
if gas spontaneously turned the paddle wheel.
Fig. 7.1: A gas in an adiabatic container fitted with a piston and a stirrer.
Each of the three sets of states that are defined above includes an infinite number
of distinct states that have a common property: their accessibility from the initial state by
adiabatic processes (adiabatic accessibility). Since adiabatic accessibility can be
measured experimentally, it is possible to give this property a name and define it in an
objective way. We call this property the entropy, S, and define it so that states that are
mutually accessible have the same entropy, those that are irreversibly accessible have
greater entropy, and those that are inaccessible have lower entropy. By changing the
initial state it is possible to define the entropy of all the states of the system. In any
adiabatic process S 0. If S = 0 the process is reversible; if S > 0 it is not. The
definition of the entropy and its monotonic behavior in adiabatic processes form the
content of the Second Law of Thermodynamics.
The concept of entropy may appear to be restricted by the fact that it was defined
for a particular type of system, the adiabatic system. In fact, this is not a restriction. An
example of an adiabatic system is an isolated system, which does not interact with its
environment at all. Any system can be made into an isolated system by joining it to the
environment with which it interacts. The composite system is adiabatic and, hence, can
only evolve in such a way that its entropy increases or remains the same. The end of its
evolution, its preferred or ultimate equilibrium state, is that which has the greatest
possible entropy.
In a very real sense the entropy is the thermodynamic measure of time. The
entropy of an adiabatic system orders its states in time. Those whose entropies are higher
must necessarily come after those whose entropies are lower. Since the entropy can only
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increase, time moves forward and cannot be reversed. The association between entropy
and time is not casual, but fundamental; the Second Law of Thermodynamics is the only
fundamental principle of theoretical physics in which time has a direction.
7.2.2 Entropy and heat
A body of material that is homogeneous in its composition and structure is called
a phase. The thermodynamic state of a homogeneous phase of a simple material, such as
the gas of Fig. 7.1, is fixed by its energy, its volume and its chemical content, that is, by
the variables E, V, and {N}. Since each state of the system has an entropy, S, the entropy
can be written as a function
S = S(E,V,{N})
7.1
of the variables that characterize the state. It is possible to choose the entropy so that the
entropy function, eq. 7.1, is a continuous function of its variables that is additive in the
sense that the joint entropy of a composite of two or more systems is the sum of their
individual entropies. Moreover, S can be defined so that the partial derivatives of the
function S(E,V,{N}) have the following simple physical values:
S
=1
E
T
7.2
where T is the absolute temperature,

S
=P
V
T
7.3
where P is the mechanical pressure, and

S
k
Nk = - T
7.4
where Nk is the mole number of the kth component and k is its chemical potential. This
definition of S is called the metrical entropy. As we shall discuss below, the entropy
function, eq. 7.1, that expresses the entropy as a function of the thermodynamic content
of the system is Gibbs' fundamental equation that governs the thermodynamic behavior
of the system.
When the entropy is given by equation 7.1 its change in an infinitesimal change of
state, that is, a change of state that involves an infinitesimal change in one or more of the
variables, E, V, and {N}, is
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S
S
S
dS = E dE + V dV + N dNk
k
1
= T (dE + PdV - kdNk)
7.5
Solving equation 7.5 for the incremental change in the energy, dE, yields the relation
dE = TdS - PdV + kdNk 7.6
k
Eq. 7.6 has a simple physical interpretation. If the state is changed quasistatically, that is, slowly enough that friction can be ignored, then the second term on the
right-hand side, -PdV, is the mechanical work done. The third term on the right is the energy due to the chemical change, {dN}, and is hence the chemical work. The energy
change that is unaccounted for is that due to the thermal interaction, the thermal work, or
heat, dQ. Hence in a quasi-static change of state
dQ = TdS
7.7
and there is a direct association between the entropy change and the heat, or thermal
work.
The association between the entropy change and the quasi-static heat that is expressed by eq. 7.7 makes it relatively easy to measure the entropy of a phase as a function
of its energy and composition. If the system is heated incrementally and quasi-statically
at constant volume and composition then the change in entropy is given by the change in
energy, which can be found independently, divided by the absolute temperature. It is also
possible to evaluate the second and third terms on the right-hand side of equation 7.6
independently, so the entropies of states that differ in volume and composition can be related to one another. Such measurements evaluate the entropy with respect to its value in
a fixed reference state. It is, however, possible to proceed further to define the absolute
value of the metrical entropy. The Third Law of Thermodynamics states that in the limit
of zero temperature the most stable state of a system is a state of perfect order whose
entropy may be set equal to zero. If this state is used as a reference the metrical entropy
is fixed to within a multiplicative constant that sets the scale of the temperature.
When the process that changes the state of the system is not quasi-static, for
example, when friction cannot be neglected, then the simple association between the heat
added and the change in the entropy is lost. Since energy is conserved and the change in
energy is equal (by convention) to the sum of the work done on the system and the heat
added to it then
dE = dQ + dW
7.8
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for any infinitesimal change of state whatever. (In the context of the First Law of
Thermodynamics eq. 7.8 is the definition of the heat.) Since non-static phenomena such
as friction or turbulence increase the energy of the system (work is done on the system by
the frictional forces or the stirring that introduces turbulence), it follows from eqs. 7.6
and 7.8 that
dW - PdV + kdNk
7.9
and hence that

dQ TdS
7.10
The entropy change is always greater than or equal to the heat added divided by the temperature. The additional entropy is due to internal changes in the system of the sort that
are caused by frictional forces or turbulence. Since these processes are inherently
irreversible, the inequality (7.10) measures the irreversibility of a change of state.
7.2.3 Entropy and randomness
The metrical entropy of a homogeneous phase of an isolated simple system can be
calculated statistically from the relation
S(E,V,{N}) = k ln(E,V,{N})
7.11
where (E,V,{N}) is the degeneracy of the phase. If the atoms contained in the system
can be treated as classical particles then the degeneracy is the total number of distinct
ways of assigning positions and momenta to the particles that are consistent with the
definition of the phase and yield the right value of the total energy. In the context of
quantum mechanics the degeneracy is the total number of distinct quantum states of the
system that are consistent with its energy and phase. We shall not prove eq. 7.11 here,
but will show that the entropy defined by 7.11 is consistent with the nature of the entropy
as we have described it.
Properties of the statistical entropy

First, eq. 7.11 predicts that the preferred phase of an isolated system is the one
that maximizes its entropy. Suppose that there are two possible phases of an isolated
system with parameters E, V, and {N}. Let the phases be designated and , and let
them have, respectively, degeneracies and . If there is no constraint on the system
that prevents it from taking on the configurations of either phase then its instantaneous
state is equally likely to be in any one of the possible states of either phase. The
probability that an instantaneous measurement of the state of the system will find it in
phase is
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P = +
7.12
which is greater than P if > , or, by eq. 7.11, if S > S. In the usual case the
system is virtually certain to be in phase if its entropy is greater; the statistical degeneracy of a state, , increases exponentially with the number of particles it contains, and
>> if it is greater at all. It follows that an isolated system evolves into the phase
(or mixture of phases) that has the highest statistical entropy.
Second, the statistical entropy is additive. Let system 1 have energy E1, volume
V1 and chemical content {N1} while system 2 has E2, V2 and {N2}. When they are separated, system 1 has degeneracy 1(E1,V1,{N1}) and system 2 has degeneracy
2(E2,V2,{N2}). The degeneracy of the two separated systems taken together is the
product
0 = 12
7.13
since each individual state in 1 can coexist with any state in 2, and conversely. Hence
the joint entropy of the separated systems is
S0 = k ln(12) = k ln(1) + k ln(2)
= S1 + S2
7.14
and the statistical entropy is additive.

Third, if two isolated systems are joined so that they interact with one another the
interaction can only increase the statistical entropy. When the two systems are joined and
interact all of the states in 1 and 2 are still possible. Since the total energy, volume
and chemical content are E = E1+ E2, V = V1 + V2 and {N} = {N1 + N2}, it is still
possible for the volume V1 to have the chemical content {N1} and the energy E1, in
which case V2 contains {N2} and E2. The total system has at least the degeneracy 12
and the entropy S1 + S2. But the interaction between the two systems creates the
possibility of new states that, depending on the nature of the interaction, correspond to
new distributions of E, V or {N}. If the interaction does result in a redistribution of E, V
or {N} the states associated with the new distribution add to the degeneracy. Hence, after
the interaction,
0 = 12
7.15
S S0 = S1 + S2
7.16
and
It follows that the statistical entropy of an isolated system can only increase.
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The statistical entropy of a system that is not isolated can also be calculated. The
method is given in standard texts on Statistical Mechanics. We limit this discussion to
the simpler, isolated system.
The statistical entropy of a solid of given energy

The degeneracy in the energy states of a typical crystalline solid has three
principle sources. First, the valence electrons in the solid can be distributed in many
different ways over the quantum states available to them, which produces the electronic
entropy, Se. The electronic entropy is much higher in a metal than in a semiconductor or
insulator. There are many empty electron states that have energies comparable to those
that are occupied by the valence electrons, and hence many distinguishable ways in
which the electrons can be distributed without changing the energy or violating the Pauli
Exclusion Principle. The electronic entropy of a semiconductor or insulator is much
smaller since almost all of the valence electrons are confined to particular atomic or
bonding states that are very nearly full.
Second, a crystalline solid has a vibrational entropy, Sv, that is due to the thermal
oscillations of its atoms about their equilibrium positions on the crystal lattice. The small
displacements associated with the lattice vibrations significantly increase the degeneracy
of the crystalline phase (the degeneracy remains finite because the motions of the
individual atoms are correlated in quantized vibrational states called phonons). The
vibrational entropy decreases with the strength and directionality of the crystal bonds,
which inhibit atom displacements, and increases with the openness of the crystal
structure. Hence very stable, high-melting solids tend to have relatively low vibrational
entropies, and metals with the more open BCC structure tend to have higher vibrational
entropies than the same metals in the close-packed structures.
Third, a multi-component solid has a configurational entropy, Sc, which is due to
the many different ways in which the various chemical species can be distributed over the
different atom sites in its structure. The number of distinct configurations is relatively
easy to calculate, and it is useful to do so. Assume that NA atoms of type A and NB of
type B are distributed over N = NA + NB atom sites. There are N! different ways of
distributing N particles over N sites (the number of permutations of an ordered list of N
objects). However, distributions that differ only through the interchange of A atoms with
one another or B atoms with one another are physically indistinguishable. Since there are
NA! ways of redistributing the A atoms over the sites occupied by A atoms in a given
configuration, and NB! ways of redistributing the B atoms, the total number of
distinguishable configurations is
N!
= N !N !
A B
7.17
If the energy of the crystal is approximately independent of the way in which the
atoms are distributed then its configurational entropy is
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Sc = k ln() = k [ln(N!) - ln(NA!) - ln(NB!)]
7.18
This expression can be simplified considerably by using Sterling's Approximation,

ln(N!) = N ln(N) - N
which is a very good approximation when N is greater than about 10.
configurational entropy can then be written
7.19
The
Sc = k [N ln(N) - NA ln(NA) - NB ln(NB)]

= - kN [x ln(x) + (1-x) ln(1-x)]
7.20
where x is the atom fraction of component A, x = NA/N.

An amorphous solid or glass has an additional entropy due to the irregularity of its
spatial configuration; the atom positions are not confined to a crystal lattice but are distributed in a less regular way. It follows that the entropy of an amorphous configuration of
atoms or molecules is always greater than that of a crystalline state of the same material.
Low-temperature behavior: the Third Law

The Third Law of Thermodynamics states that the entropy of the preferred, or
ultimate equilibrium phase of a system vanishes in the limit of zero absolute temperature.
This is equivalent to the statement that the ground state of the system, the state of lowest
energy, is unique (non-degenerate).
The electronic and vibrational entropies vanish naturally at zero temperature. The
electrons are reduced to their ground state. While the atoms continue to vibrate in the
zero-temperature limit, these ground state vibrations are quantum phenomena that have
no entropy since they are associated with a single quantum state. However, the
configurational entropy is independent of the temperature. It vanishes at zero
temperature only if the solid takes on a perfectly ordered state that has no configurational
entropy. This leads to the important conclusion that the preferred state of a solid at low
temperature is a perfectly ordered crystal or macromolecule.
7.3 THE CONDITIONS OF EQUILIBRIUM

7.3.1 The equilibrium of an isolated system
If the entropy of an isolated system can be increased by an infinitesimal change in
its state, then that change will inevitably occur. The reason is that any real system is in
constant thermal agitation on a microscopic scale. Through local fluctuations it
constantly samples thermodynamic states that are incrementally close to whatever
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macroscopic state it is currently in. If any of these nearby states have higher entropy the
system reaches them, but then cannot return. It necessarily evolves in the direction of
increasing entropy. Its evolution continues until it finds itself in a state that provides a
local extremum in the entropy such that no infinitesimally adjacent state increases the
entropy further. The states that correspond to local extrema in the entropy can be
maintained, at least momentarily, and are hence possible equilibrium states. They satisfy
a condition of equilibrium that can be written
(S)E,V,{N} 0
7.21
where S is the infinitesimal change in the entropy that would result if the state of the
system were changed infinitesimally at the given values of E, V and {N}, and the
inequality holds for every possible infinitesimal change.
There are four kinds of equilibria that satisfy the condition expressed in the
inequality 7.21, of which only two are of any real interest. The four are illustrated in Fig.
7.2, where we have assumed that a single parameter, x, describes the path between states
in order to make a two-dimensional plot (since the possible states differ in microstructure
their differences are described by many independent variables; the entropy should be
plotted in a multi-dimensional space).
metastable
unstable
stable
Fig. 7.2: Illustration of four kinds of equilibrium: metastable, unstable

(inflection point), unstable (minimum), and stable equilibrium.
A local minimum or saddle point in the entropy creates a state of unstable equilibrium. Such states satisfy the mathematical condition for equilibrium but cannot be preserved in practice since they are unstable under small, finite perturbations. A local maximum in the entropy defines a state that is stable with respect to small changes and can, in
principle, be preserved for a very long time. However, if the locally stable state does not
provide the maximum entropy for all possible states of the system then it will transform if
it is given a sufficiently large perturbation in the right direction. Such states are called
metastable states. They must eventually evolve to the state of maximum entropy , or
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stable equilibrium state, since the natural fluctuations of the system will eventually cause
an appropriate perturbation, however large that perturbation must be. How long a
metastable state can be preserved is a kinetic issue that depends on the size of the
perturbation that is required to change it and the frequency with which perturbations
occur. Many engineering materials are used in metastable states that are preserved
almost indefinitely, including all amorphous materials and glasses and many crystalline
solids.
7.3.2 Internal equilibrium
The general condition of equilibrium, equation 7.21, leads to specific conditions
of thermal, mechanical and chemical equilibrium that are satisfied in all equilibrium
states. To find the conditions of internal equilibrium we consider two subsystems of the
system that have volumes V1 and V2, energies E1 and E2 and chemical contents {N1}
and {N2}, and are in contact with one another, as illustrated in Fig. 7.3. If the system is
to be in equilibrium its entropy must not increase if the energy, volume or chemical
content of the two subsystems is redistributed between them.
Fig. 7.3: Two subsystems within an isolated system that interact only
with one another.
Thermal equilibrium
First let the two subsystems exchange an infinitesimal amount of energy without
changing the volume or chemical content of either. This exchange describes a thermal
interaction. Since energy is conserved the energy gained by subsystem 1 must be lost by
subsystem 2. Hence
dE2 = - dE1
7.22
By eq. 7.5 the total entropy change in the process is

dE1
dE2
dS = dS1 + dS2 = T + T
1
2
1
1
= dE1T - T
1
2
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where T1 and T2 are the temperatures of the two subsystems. Eq. 7.23 shows that the
system can only be in equilibrium if T1 = T2. If this is not the case then dS is positive for
a transfer of energy from the high-temperature subsystem to the low-temperature one.
Hence the two subvolumes are not in equilibrium with one another unless their temperatures are the same.
The same reasoning applies to any choice of subvolumes within the system. It
also applies when the system is not isolated, since a system cannot be in equilibrium if it
is out of equilibrium with respect to internal changes that do not affect its environment.
We are therefore led to the condition of thermal equilibrium, which holds in general: a
system in equilibrium has a uniform temperature.
T = const.
7.24
Mechanical equilibrium
A second possible interaction between two subsystems is a mechanical interaction
in which they distort one another. Mechanical interactions in a solid can be rather
complicated; they may be elastic in the sense that they stretch the bonds without
rearranging the atoms, or plastic, in the sense that the atoms are permanently displaced.
We will discuss these deformations at a later point in the course. However, if the system
is in mechanical equilibrium then it must at least be in equilibrium with respect to the
simple, fluid-like mechanical interaction that exchanges volume between the two
subsystems by displacing the boundary between them, and must satisfy the condition of
mechanical equilibrium that governs that interaction.
Even then the mechanical interaction is complicated by the presence of external
fields, such as the gravitational field, that impose mechanical forces directly on the
material. However, external fields, including the gravitational field, have a negligible
effect in most situations and we shall ignore them (the usual negligibility of gravity is one
reason why materials processing in space has turned out to be less attractive than many
had hoped, although there are potential applications that may prove important).
Assuming fluid-like deformation and neglecting external fields, the mechanical
interaction displaces the boundary between the two subvolumes so that
dV2 = - dV1
7.25
Since energy is conserved (dE2 = - dE1) and temperature is constant (thermal

equilibrium), the associated change in the entropy is
dV1
1
dS = T [P1dV1 + P2dV2] = T [P1 - P2]
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If P1 P2, dS is positive when the volume of the high-pressure subsystem increases at the
expense of that of the low-pressure one. We are hence led to the condition of mechanical
equilibrium in the absence of external fields: a system in mechanical equilibrium in the
absence of external fields has a uniform pressure.
P = const.
7.27
Chemical equilibrium
The third type of interaction between the two subsystems is a chemical interaction
in which they exchange matter. Since any one of the independent chemical components
may be exchanged there is a separate condition of chemical equilibrium for each. As in
the case of mechanical equilibrium, the conditions of chemical equilibrium are affected
by external fields since external fields such as the gravitational field apply forces to the
individual atoms that do work when they are moved. We assume that external fields can
be neglected.
Since the total amount of the kth component is conserved, the quantity added to
V2 is equal to that lost from V1,
2
dNk = - dNk
7.28
Letting the exchange occur at constant volume (we have already found the condition of
mechanical equilibrium) the entropy change at constant total energy and uniform
temperature is
1 1 1
1 1
2 2
2
1
dS = - T kdNk + kdNk = - T k - k dNk
i
7.29
1
where k is the chemical potential of the kth component in the ith subsystem. If k
2
k the entropy increases if a quantity of the kth component is transferred from the
system of higher chemical potential to that in which the potential is lower. We are
therefore led to the condition of chemical equilibrium in the absence of external fields: a
system in chemical equilibrium in the absence of external fields has a uniform value of
the chemical potential of each of its components.
k = const.
7.30
7.3.3 Non-equilibrium states; constrained equilibria

The materials that are used in engineering are not usually in equilibrium states,
even in the sense of metastable equilibrium. They are in non-equilibrium states that
evolve continuously. The materials can be used as if their properties were constant only
because the rate of evolution is so slow that it can be neglected.
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A familiar example of a non-equilibrium material is a semiconductor that has

been chemically doped to create islands that contain local concentrations of electrically
active solutes. The chemical potentials of the solute species are not uniform; the material
evolves toward an equilibrium state in which the solutes are spread uniformly through the
semiconductor crystal. However, non-equilibrium behavior can ordinarily be neglected
because the materials are used at relatively low temperature where the rate of solute
diffusion is so slow that the solute distribution changes very little over the useful life of
the device.
A second example is a polygranular crystalline solid. The crystal grains never
have equilibrium shapes. Their surfaces tend to become slightly curved to achieve local
mechanical equilibrium. It can be shown that the chemical potential is slightly higher on
the convex side than on the concave side of the grain boundary. Atoms move across the
grain boundary in response to the chemical potential gradient so that the grain boundary
migrates toward its center of curvature. The smaller grains disappear with time and the
average grain size grows. However, at the normal temperatures at which polygranular
materials are used the rate of grain growth is negligible.
A third example is a crystalline solid that contains dislocations. The dislocations
are non-equilibrium defects. They exert forces on one another and, given sufficient time,
move by glide and climb to annihilate by interacting with one another or with free
surfaces. Again, this process is very slow at ordinary temperatures, so the dislocation
distribution is nearly fixed in the absence of mechanical forces that are large enough to
force dislocation motion.
To apply thermodynamics to the behavior of non-equilibrium systems like these,
which include almost all real materials, we treat them as idealized systems in constrained
equilibria, that is, we analyze the behavior of a hypothetical system that is physically
similar to the material of interest, but includes physical constraints that maintain it in
thermodynamic equilibrium. Formally, we replace the kinetic constraints that maintain
the non-equilibrium state by imaginary physical constraints that accomplish the same
purpose in a static way. For example, an idealized polygranular solid whose grain
boundaries are rigid, impermeable membranes behaves in many ways like a real
polygranular solid, but its grains cannot grow. One can gain insight into the
thermochemical behavior of polygranular solids by considering the behavior of solids
with impermeable grain boundaries, which can reach thermodynamic equilibrium in the
polygranular state. A silicon crystal in which certain regions have been doped with
active solutes behaves at low temperature very much like a hypothetical crystal in which
the doped regions are surrounded by impermeable membranes. The low-temperature
thermochemical behavior of a dislocated solid is very much like that of a hypothetical
solid whose dislocations are artificially pinned in space.
We implicitly use constrained equilibrium models of this sort almost whenever
we apply thermodynamics to real systems. The constraints fix those non-equilibrium
features of the microstructure that remain nearly constant with time. The conditions of
equilibrium govern those features of the microstructure that are kinetically capable of
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reconfiguration during the time of experimental interest. The microstructural evolution

of a real solid can be incorporated in this kind of model by periodically relaxing the
hypothetical constraints so that the grains can grow, the solutes migrate or the
dislocations move.
7.4 THE THERMODYNAMIC POTENTIALS

The condition of maximum entropy is sufficient to analyze the equilibrium states
of any system; it applies to an isolated system, and any system can be made part of an
isolated system by joining it to its environment. However, it is usually inconvenient to
do this. An engineering material is almost never used in a condition that can be regarded
as isolated. It interacts with its environment. The relevant isolated system is a composite
system that contains both the material and the environment that interacts with it. But the
physical nature of the environment is rarely of interest. In engineering practice the
"environment" may be nothing more than a heat source, such as an oven or furnace, that
is used to maintain temperature, or a mechanical linkage that maintains the load on a
material that is used as a structural member, or an electrical condenser that sets the
electric field in a material that is used as a capacitor. Its only function is to establish the
conditions under which the material is used; its detailed internal state is uninteresting. If
the environment is regarded as part of the system to which the conditions of equilibrium
are applied then one has to worry about it. It is far preferable to find an alternate way of
phrasing the conditions of equilibrium so that they can be applied to a system that is not
isolated, and involve only the state of the material itself.
We accomplish this by representing the environment as a thermodynamic
reservoir. A thermodynamic reservoir is a system that is so large compared to the system
of interest that it can interact by exchanging energy, volume or chemical species without
its own state being affected in any sensible way. The reservoir is assumed to be in
equilibrium to the extent that it has a well-defined temperature, pressure and set of
chemical potentials. Since its state is unaffected by its interaction with the system the
values of these intensities remain constant, and the reservoir serves to fix their values
within the system. When the environment can be approximated as a reservoir it is always
possible to treat the behavior of the system in terms of its own properties and
thermodynamic states without reference to the physical nature of the environment.
However, when the environment is treated as a reservoir the thermodynamic
quantity that governs the equilibrium of the system is not its entropy, but an appropriate
thermodynamic potential whose identity depends on the nature of the interaction between
the system and environment. The thermodynamic potentials that are most often useful
are the Helmholtz free energy, which governs the equilibrium of a system with fixed
volume and chemical content that interacts with a thermal reservoir, and the Gibbs free
energy, which governs the equilibrium of a system with fixed composition that interacts
with a reservoir that sets both its temperature and its pressure. Other common potentials
include the enthalpy, which governs a system of fixed entropy and composition that
interacts with a pressure reservoir (the enthalpy is frequently used in fluid dynamics, but
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rarely in materials science), and the work function, which governs the behavior of an
open system, a system that is enclosed by imaginary boundaries that fix its volume, and
interacts with a reservoir that sets its temperature and chemical potentials.
The various thermodynamic potentials are readily defined by considering the various experimental situations to which they naturally apply. Solids are ordinarily used in
one of three experimental situations.
First, a solid of given composition and volume has its temperature controlled by a
reservoir. An example is a material that is heated in a furnace, when we can neglect the
thermal expansion of the solid and the possibility of chemical interaction with the atmosphere in the furnace. In this case the controlled variables are V, {N} and T, and, as we
shall see, the relevant thermodynamic potential is the Helmholtz free energy, F = E - TS.
Second, and more realistically, the solid has a constant composition, but has both
its temperature and pressure controlled by the environment. The temperature may be
controlled by a furnace, or, simply, by ambient air, and the pressure may be fixed by the
ambient, or by some mechanical device that loads the solid. In this case controlled
variables are T, P and {N}, and the relevant thermodynamic potential is the Gibbs free
energy, G = E - TS + PV.
Third, the solid has a fixed size and shape, and its temperature and chemical
potentials controlled by its environment. The common example is a small subvolume
within a larger body, which we define by simply drawing an imaginary boundary around
it. This open system has fixed volume, but can freely exchange energy and matter with
its environment. In this case the controlled variables are T, V and {} (the set of
chemical potentials), and the relevant thermodynamic potential is the work function, =
E - TS - kNk. We consider each case in turn.
Consider a system that has fixed volume, V, and chemical content, {N}, and is in
contact with a reservoir with fixed temperature, T. The system and reservoir together
form an isolated system as shown in Fig. 7.4. The system can exchange energy with the
reservoir through a thermal interaction across its boundary, but the boundary is rigid and
impermeable.
The system (1) and reservoir (2) together make up an isolated system. By eq.
7.21 the system is in equilibrium only if every possible infinitesimal change of state leads
to a decrease in the entropy, that is, if (eq. 7.21)
(S)E,V,{N} 0
7.21
Assume an infinitesimal transfer of energy (E) between the system and the reservoir. The reservoir acquires the energy increment E2 = - E1. The total entropy change
in the system is S1, which may include an entropy increment due to internal changes as
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well as that associated with the energy transfer. The entropy change in the reservoir may
also include internal changes, but these must be positive, and hence cannot affect the
equilibrium of the system. We can, therefore, neglect them and use eq. 7.5 to write
E2
E1
S2 = T = - T
7.31
T
{N},V
dE
Fig. 7.4: A system of fixed volume and composition that is in contact

with a thermal reservoir.
The total entropy change is
E1
1
S = S1 - T = - T[E1 - TS1]
1
= - T [E1 - TS1] 0
7.32
where the last form of the right-hand side follows since T is constant. Defining the quantity
F1 = E1 - TS1
7.33
and using the fact that the temperature, T, is constant and the same in the system and the
reservoir, the condition of equilibrium becomes
(F1)T,V,{N} 0
7.34
The quantity F = E -TS is called the Helmholtz free energy. Eq. 7.34 states that if
a system with fixed volume and chemical composition interacts with a thermal reservoir,
its behavior is governed by its Helmholtz free energy, F, which has a minimum value for
an equilibrium state.
It is useful to examine the functional dependence of the Helmholtz free energy.
Using eq. 7.6, the total differential of F is
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dF = dE - d(TS) = TdS - PdV + kdNk - TdS - SdT

k
= - SdT - PdV + kdNk
7.35
If the Helmholtz free energy is evaluated as a function of the temperature, T, volume, V,

and composition, {N}, as
F = F(T,V,{N})
7.36
F
F
F
dF = T dT + V dV + N dNk
k
7.37
then
It follows by comparison with equation 7.35 that

F
=-S
T
7.38
F
=-P
V
7.39
Nk = k
7.40
which show the dependence of the Helmholtz free energy on its natural variables, T, V
and {N}.
7.4.2 The Gibbs free energy
dV
{N}
P, T
dE
Fig. 7.5: A system with fixed composition, {N}, that is in mechanical

and thermal contact with a reservoir with fixed P and T.
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In a second common situation (which is, ordinarily, more realistic) the system has
a given chemical content, but interacts with a reservoir that fixes both its temperature and
pressure. This case is diagrammed in Fig. 7.5. The system can exchange volume and energy with the reservoir through mechanical and thermal interactions at its boundary, but
the boundary is impermeable.
As in the previous example, the system (1) and reservoir (2) together make up an
isolated system, which is in equilibrium only if every possible infinitesimal change of
state leads to a decrease in the entropy. Assume an infinitesimal transfer of energy (E)
between the system and the reservoir that is accompanied by an infinitesimal
displacement of the boundary so that the volume of the system changes by V. The
reservoir acquires the energy increment E2 = - E1 and the volume increment V2 = V1. The total entropy change in the system is S1. The relevant entropy change in the
reservoir can be written, according to eq. 7.5,
1
1
S2 = T[E2 + PV2] = - T[E1 + PV1]
7.41
Hence the total entropy change is

1
1
S = S1 - T[E1 + PV1] = - T[E1 - TS1 + PV1]
1
= - T [E1 - TS1 + PV1] 0
7.42
where the last form of the right-hand side follows since T and P are constant. Defining
the quantity
G1 = E1 - TS1 + PV1
7.43
and using the fact that T and P are constant, the condition of equilibrium becomes
(G1)T,P,{N} 0
7.44
The quantity G = E -TS + PV is called the Gibbs free energy. Eq. 7.44 states that
if a system with fixed chemical content interacts both thermally and mechanically with a
reservoir that fixes its pressure and temperature, its behavior is governed by its Gibbs free
energy, G, which has a minimum value for an equilibrium state.
The functional dependence of the Gibbs free energy can also be found with the
help of eq. 7.6. The total differential of G is
dG = dE - d(TS) + d(PV)
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= - SdT + VdP + kdNk
7.45
If the Gibbs free energy is written as a function of the temperature, T, pressure, P, and
composition, {N}, as
G = G(T,P,{N})
7.46
then
G
G
dG = T dT + P dP +
k
Nk dNk
7.47
It follows by comparison with eq. 7.45 that

G
=-S
T
7.48
G
=V
P
7.49
Nk = k
7.50
which show the dependence of the Gibbs free energy on its natural variables, T, P and
{N}.
In real systems the environment usually fixes the pressure and temperature, so the
Gibbs free energy is the pertinent thermodynamic potential. However, when the system
is a solid at atmospheric pressure, which is the case that is most frequently of interest, the
PV term is almost always negligible compared to F and there is virtually no numerical
difference between the Gibbs and Helmholtz free energies.
7.4.3 The work function
T, {}
V
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dN
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Fig. 7.6:
Fall, 2008
An open system, with fixed volume, in contact with a reservoir that fixes T and {}.
We are often interested in behavior in the interior of a material. Since regions in

the interior of a material can, ordinarily, exchange both energy and chemical content with
one another, the best way to study their behavior is usually by defining an open system,
of the kind diagrammed in Fig. 7.6. A volume within the material is surrounded by an
imaginary boundary. Since the boundary is fixed in space, its volume is given.
However, its energy and chemical content are not. The material beyond the boundary
acts as a thermal and chemical reservoir that fixes the temperature and chemical
potentials within the system.
Again, the combination of system (1) and reservoir (2) make up an isolated
system, which is in equilibrium only if every possible infinitesimal change of state leads
to a decrease in the entropy. Assume an infinitesimal transfer of energy (E) that may be
accompanied by infinitesimal transfers (Nk, k = 1,...,n) of each of the n chemical species
present. The reservoir acquires the energy increment E2 = - E1 and the chemical
2
1
additions Nk = - Nk , k = 1,...,n. The total entropy change in the system is S1. The
entropy change in the reservoir is (eq. 7.5),
1
1
2
1
S2 = TE2 - kNk = - TE1 - kNk
k
k
7.51
Hence the total entropy change is

1
1
1
1
S = S1 - TE1 - kNk = - TE1 - TS1 - kNk
k
k
1
1
= - T E1 - TS1 - kNk 0
7.52
where the last form of the right-hand side follows since T and the chemical potentials, k,
are held constant by the reservoir. Defining the work function,
= E - TS - kNk
7.53
the condition of equilibrium becomes

()T,V,{} 0
7.54
Eq. 7.54 states that if a system with fixed boundaries interacts both thermally and chemically with a reservoir that fixes the temperature and chemical potentials its behavior is
governed by its work function, , which has a minimum value for an equilibrium state.
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Using eq. 7.6, the total differential of is
d = dE - d(TS) - d kNk
k
= - SdT - PdV - Nkd k
7.55
If the work function is written as a function of the temperature, T, volume, V, and

chemical potentials, {}, as
= (T,V,{})
7.56
then

d = T dT + V dV + dk
k
7.57
It follows by comparison with eq. 7.55 that
=-S
T
7.58
=-P
V
7.59
G
=N
k
k
7.60
which show the dependence of the work function on its natural variables.
A fourth thermodynamic potential, the enthalpy,
H = E + PV
7.61
governs the behavior of systems whose entropy, pressure, and chemical content are controlled. This is seldom the situation in Materials Science, where the enthalpy is rarely
used for any purpose other than as a shorthand notation for the sum E + PV. However,
the enthalpy is often the preferred potential in fluid mechanics, since entropy is locally
conserved in many types of fluid flow.
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7.5 THE FUNDAMENTAL EQUATION

The various thermodynamic functions defined in the previous section are different
and equivalent forms of the fundamental equation of the system. The fundamental
equation is a concept introduced by Gibbs, who recognized that there is a single
thermodynamic function that contains a complete description of the thermodynamic state
of a material, provides values for all of its thermodynamic properties, and governs
equilibrium.
7.5.1 The entropy function
The entropy function,
S = S(E,V,{N})
7.62
is the form of the fundamental equation that is provided directly by the Second Law of
thermodynamics. It is the most convenient form of the fundamental equation when the
system of interest is isolated (or adiabatic). It then has the following features.
First, the natural variables of the entropy function, E, V and {N}, are precisely the
variables that can be controlled experimentally when the system is isolated. Their values
are fixed by setting the content of the system at the time it is isolated, and cannot be
altered afterwards.
Second, the values of E, V, {N} are sufficient to fix the equilibrium state of an
isolated system. The Second Law asserts that the equilibrium state has a maximum value
of the entropy, S, with respect to all other ways of configuring the system with the given
values of E, V and {N}. The entropy function, 7.62, is just the function that gives the entropy of the equilibrium state as E, V and {N} are varied. Of course, there may be
physical or kinetic constraints on the system that limit the configurations it can take on,
and set it in a metastable equilibrium state or a constrained equilibrium state. In that case
the entropy function incorporates the constraints; the entropy has the largest value it can
have for given E, V, and {N} when those constraints are imposed.
Third, the conjugate forces, T, P and {}, are determined by the first partial
derivatives of the entropy function
S
=1
E
T
7.63
S
=P
V
T
7.64
= - k
Nk
T
7.65
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That is, each thermodynamic force is specified by the partial derivative of the entropy
function with respect to the thermodynamic quantity that is conjugate to it.
Fourth, the thermodynamic properties of the system are specified by the second
and higher derivatives of the fundamental equation. The thermodynamic properties are
material properties that govern the changes in the thermodynamic contents, E, V, and
{N}, with the values of the thermodynamic forces. The most commonly used are the
specific heat, which governs the change of energy with temperature, the compressibility,
which governs the change of volume with pressure, and the coefficient of thermal
expansion , which governs the change of volume with temperature. The thermodynamic
properties are discussed in more detail in the following section.
Finally, the fundamental equation can be transformed so that its independent variables are changed from the set E, V and {N} to some other set that is more natural for a
particular experimental situation. The simplest transformation is accomplished by
solving the entropy function for the energy. The result is the energy function,
E = E(S,V,{N})
7.66
which, as we shall see, contains precisely the same information as the entropy function,
but with the different set of independent variables {S,V,{N}} replacing {E,V,{N}}.
Since the energy function contains the same information, it is also a form of the
fundamental equation. Other useful forms of the fundamental equation are obtained by
applying a technique known as the Legendre transform to the energy function. The
various Legendre transforms of the energy function are the thermodynamic potentials we
discussed in the previous section.
7.5.2 The energy function
The independent variables that appear in the energy function (7.66) are the set S,
V and {N}. While we shall not prove it here, it is a consequence of the Second Law that
the energy of an equilibrium state has the minimum value that it can have for any way of
reconfiguring the system at given values of S, V and {N}. This is the energy minimum
principle, which you have probably encountered fairly frequently in elementary physics.
It is the complement of the entropy maximum principle that the entropy has the largest
possible value for given E, V and {N}. The thermodynamic quantities S, V and {N} that
appear as independent variables in the energy function (7.66) characterize the system; the
equilibrium state of the system is that which has the least value of the energy for the
given values of S, V and {N}. The function E(S,V,{N}) gives the minimum
(equilibrium) value of the energy.
While it is not easy to construct experimental systems in which the entropy is controlled, there are hypothetical situations in which the variables S, V and {N} are fixed,
and these are important in theoretical analysis. First, in the limit of low temperature the
Third Law of thermodynamics asserts that the entropy of a system approaches a least
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value that is independent of V and {N}; in this limit the value of the entropy is fixed.
Since it is much easier to compute the energy of a solid than its entropy, most of the
available theoretical analysis of the solid state concerns the identification and properties
of minimum energy states. Since many stable crystalline solids assume their minimum
energy structures at temperatures well above room temperature, this approach is often
fruitful. In many other cases we can usefully discuss the properties of solids at finite
temperature by identifying the properties of the minimum-energy state and inferring the
changes that should occur as the temperature is raised. We have already used this
approach to discuss the electronic configurations of atoms and solids in terms of their
minimum-energy, ground states.
The change in the energy in an infinitesimal change in the state is
dE = TdS - PdV + kdNk 7.67
k
where the successive terms on the right-hand side correspond to the thermal, mechanical
and chemical work done if the change of state is accomplished without turbulence or friction. Note that each term in this expression has the form of a thermodynamic force, T, P
or k, multiplied by the differential change in one of the thermodynamic quantities, S, V
or Nk. Each of the forces, f = T, P or k, is said to be conjugate to the corresponding
quantity, x = S, V or Nk, in that the work done by that force in an infinitesimal change of
state is obtained by multiplying it by the differential change in its conjugate quantity.
To complete the specification of the state of a system that has given values of S,
V and {N} we need to know the values of the conjugate forces, T, P and {}. These are
determined from the fundamental equation by the first partial derivatives of the energy
function
E
=T
S
7.68
E
=-P
V
7.69
Nk = k
7.70
That is, each thermodynamic force is given by the partial derivative of the function
E(S,V,{N}) with respect to its conjugate quantity.
The thermodynamic properties of the system are the materials properties that
govern the changes in the values of the thermodynamic forces with a change of state. For
example, the isometric specific heat, CV, governs the change in the temperature with a
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differential change in the energy at constant volume and composition according to the
relation
dE
dT = C
7.71
while the isentropic compressibility, S, gives the change in pressure on a differential

change in volume at constant entropy and composition according to the relation
dV
dP = V
7.72
These and the other first-order thermodynamic properties of the system are given
by the second partial derivatives of the energy function. For example,
2E
T
T

S2 = SV{N} = CV
7.73
where the subscripts on the partial derivative indicate that it is to be taken at constant volume and composition, and the final form of the right-hand side follows from the fact that
if a sample is heated reversibly at constant V and {N} the change in entropy is
CVdT
dQ
dE
dS = T = T = T
7.74
The isentropic compressibility is given by the second derivative of the energy function
with respect to the volume,
2E
P
1

V2 = - VS{N} = VS
7.75
where the isentropic compressibility is defined as

1 V
S = - V P
7.76
S{N}
If the system is an n-component fluid there is a total of (n+2)2 second partial derivatives,
1
of which only 2(n+2)(n+3) are independent since the value of a second partial derivative
is independent of the order of differentiation. The only other first-order thermodynamic
property that is commonly given a name is the isentropic coefficient of thermal
expansion,
1 V
S = V T
7.77
S{N}
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This property is related to the cross-derivative of the energy with respect to entropy and
volume:
2E
T
1
SV = VS{N} = VS
The third and higher derivatives of the energy function are higher order thermodynamic properties that determine how the first-order thermodynamic properties vary with a
change in state.
To recapitulate, the energy function is a form of the fundamental equation. Its independent variables are a sufficient set of thermodynamic quantities to determine the
thermodynamic state. Its first partial derivatives with respect to these quantities give the
thermodynamic forces. Its second and higher partial derivatives give the thermodynamic
properties of the system. Moreover, the fundamental equation determines the conditions
of equilibrium for a system in which the variables S, V and {N} are experimentally
controlled; by the minimum energy principle the energy has a minimum value for all
possible changes in the state of the system that maintain the total values of these
quantities.
7.5.3 Alternate forms of the fundamental equation
Ordinarily the variables that are controlled when a material is processed, used, or
experimented on are some mixture of thermodynamic forces and quantities. For
example, when the system is in a rigid, impermeable, diathermal container, T, V and {N}
are controlled.
Note, however, that one can never control a thermodynamic force and its
conjugate thermodynamic quantity at the same time; to control the temperature of a
system it must interact thermally with a reservoir, and hence its entropy cannot be
controlled, to control the pressure it must interact mechanically with a reservoir, and
hence its volume cannot be controlled, to control its chemical potential it must interact
chemically, and hence the composition cannot be controlled. More generally, if we
divide the thermodynamic variables into the conjugate pairs (S,T), (V,P), (Nk,k) then we
can control only one variable within each conjugate pair during an experiment.
As we have already seen, it is useful to express the condition of equilibrium for a
given experimental situation in terms of the minima of that thermodynamic potential
whose natural variables are the variables that are controlled experimentally (maxima in
case of the entropy of an isolated system). We can now see that when these
thermodynamic potentials are written as functions of their natural variables they are
alternate forms of the fundamental equation.
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Consider, for example, the Gibbs free energy, which governs the equilibrium of a
fluid system whose temperature, pressure and composition are controlled. In terms of its
natural variables, the Gibbs free energy is given by the function
G = E - TS + PV = G(T,P,{N})
7.79
We have already found that the first partial derivatives of the Gibbs free energy are
G
=-S
T
7.48
G
=V
P
7.49
Nk = k
7.50
Hence the thermodynamic quantities and forces that are not fixed by the experimental
situation are determined by the first derivatives of the Gibbs free energy function.
The second derivatives of the Gibbs free energy function given the first-order
thermodynamic properties. These appear in a slightly different form from those derived
from the energy function. For example, the second partial derivative of the Gibbs free
energy with respect to the temperature is
2G

CP
= G = - S
=
T2
T T
T P{N}
T
7.80
which defines the isobaric specific heat, CP, rather than the isometric specific heat, CV.
The second derivative of G(T,P,{N}) with respect to the pressure is
2G

= G = V
P T{N} = - VT
P2
P P
7.81
where T is the isothermal compressibility,

1 V
T = - V P
7.82
T{N}
The cross-derivative of G(T,P,{N}) with respect to temperature and pressure is

2G
= G = V
TP
T P{N} = VT
T P
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where T is the coefficient of thermal expansion,

1 V
T = V T
P{N}
7.84
While the thermodynamic properties defined by second derivatives of the Gibbs

free energy function differ slightly from those derived from the energy function, it can be
shown that these (and the properties defined by the second derivatives of any other
thermodynamic potential) can be derived from those defined by the second derivatives of
the energy function. There is a general mathematical method for doing this, called the
Jacobian method, which we shall not review here.
The same results follow for any of the other thermodynamic potentials defined in
the previous section. When they are written as function of their natural variables their
first derivatives give the values of the thermodynamic forces and quantities that are
conjugate to the set of independent variables, and the second and higher partial
derivatives give the thermodynamic properties. When the natural variables of a given
thermodynamic potential are the variables that are experimentally controlled, that
potential governs the equilibrium of the system.
Hence, as Gibbs recognized, the problem of determining the macroscopic equilibrium behavior of a material is reduced to the problem of finding its fundamental equation.
This can be done experimentally, or, in principle, theoretically using the methods of
statistical thermodynamics.
7.5.4 The integrated form of the fundamental equation
The energy of a system can be written in the integrated form
E = TS - PV + kNk
7.85
To prove this equation, we use the fact that E, S, V and N are all additive quantities. If
we double the size of the system without changing its internal state, we simply double the
value of each. However, the energy is a function of S, V and {N}, E = E(S,V,{N}). This
function must have the mathematical property that, if we multiply each of the
independent variables, S, V, and {N}, by the same constant, , the energy is also
multiplied by . That is,
E(S,V,{N})
= E(S,V,N) = E
7.86
Functions that have this property are called homogeneous functions of the first order. If
we now differentiate both sides of eq. 7.86 with respect to (which we can do, since
can be any number), the result is
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S + E V + E N = E
(S)
(V)
(Nk) k
7.87
Since eq. 7.87 holds for any value of , it holds if = 1. Setting = 1 and using eqs.
7.68-70 yields eq. 7.85.
Given eq. 7.85, the integrated forms of the other common thermodynamic potentials are:
F = E - TS = - PV + kNk
7.88
G = E - TS + PV = kNk
7.89
= E - TS -
kNk = - PV
7.90
Eq. 7.90 reveals why is called the work function of the system; it is given by
the product of pressure and volume. Eq. 7.89 shows that the Gibbs free energy is
associated with the total chemical energy of the material.
7.5.5 The statistical form of the fundamental equation
One can, in principle, calculate the fundamental equation of a material by
applying the techniques of Statistical Thermodynamics. In the formal sense, these are
straight-forward, and were introduced in Section 7.2.3 when we discussed the relation
between the entropy and the degeneracy, or randomness of the system. In that case we
considered a material that was isolated from its environment, so that its energy, E,
volume, V, and composition. {N} were fixed. Suppose that we are able to identify every
state that this material can possibly have, consistent with the rules of quantum mechanics.
The possible states include the various ways of configuring the ion cores into static
equilibrium configurations, the various ways of distributing the electrons among the
allowable electron states for a given distribution of the ion cores, and the possible
vibrational states of the ion cores about their equilibrium positions, under the restriction
that all of these states have the same energy, E. If the number of these states (the
degeneracy of the system) is (E,V,{N}), then the entropy is given by
S(E,V,{N}) = k ln(E,V,{N})
7.11
and we have evaluated the fundamental equation of the material. The problem, of course,
is counting all the states. This is always a difficult exercise, and is made particularly
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difficult by the restriction that the states must have the same energy. When the
configuration of atoms or electrons is changed, the energy ordinarily changes as well.
It is almost always easier to evaluate the Helmholtz free energy, F(T,V,{N}). To
do this we let the material have a given volume and composition, but let it exchange
energy with a reservoir that fixes its temperature. In this case the state of the material can
have any energy, provided that it has the given volume and composition. Let an arbitrary
state be denoted by the index, n, and let the material have energy, En, when it is in its nth
state. To compute the fundamental equation of the solid we form the canonical partition
function,
- En
Z(T,V,N) = e
7.91
where the coefficient, = 1/kT and the sum is taken over all admissible states. The partition function, Z, is a function of T, V and N since the energy of the nth state depends on
the volume of the system and the number of particles, while the coefficient, , is the
reciprocal temperature. The Helmholtz free energy, F(T,V,N), is obtained directly from
the partition function by the relation
F(T,V,N) = - kT ln[Z(T,V,N)]
7.92
Once the Helmholtz free energy has been found all other thermodynamic potentials and
properties can be computed from it.
The statistical relations that evaluate the fundamental equation, eqs. 7.91-92, are
formally simple. The problem is to identify and compute the energies of all the possible
states, which is not simple at all. While a number of interesting problems have been
solved, at least approximately, with the techniques of statistical thermodynamics, in
almost all cases the thermodynamic properties of real materials must be measured
experimentally.
7.6 THE THERMODYNAMICS OF SURFACES

External surfaces and internal interfaces in solids influence their behavior in many
important ways. Their energies influence the shapes of solids, including grains and
phases within solids, and, as we shall see in a later chapter, have a strong influence on
whether and where a new phase will form when it is thermodynamically favorable for it
to do so. Their permeability controls the exchange of material from phase to phase.
Interfaces often have chemical content of their own. Adsorbed species influence the
reactivity of a solid, and may strongly affect its mechanical properties. For example,
superficially minor concentrations of metalloid impurities in structural metals, such as
sulfur or phosphorous in steel, can cause catastrophic embrittlement when they are
adsorbed on grain boundaries.
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The thermodynamics of interfaces is made difficult by their complex structure.

The interfaces that separate phases in contact are not strict discontinuities. They are
rather thin transition shells across which the materials properties and thermodynamic
densities change from the values appropriate to one phase to those appropriate to the
other. The reason for the thickness of the interface is relatively straightforward: the two
phases perturb one another over a distance that is at least equal to the effective range of
atomic interaction. Even in the simplest case, a crystalline solid that presents a closepacked surface to a vacuum, the atomic packing of the first few layers below the surface
is distorted; there is an asymmetry in bonding since there are no atoms beyond the
surface. The interface structure is difficult to predict, and often impossible to observe.
Even the best modern characterization tools reveal very little about the internal structure
of real interfaces. We are hence faced with the problem of describing the behavior of an
inhomogeneous material whose internal structure we know very little about.
The thermodynamics of surfaces was developed by Gibbs (Equilibrium of Heterogeneous Substances), who devised a mathematical technique that acknowledges the finite
thickness of the interface while avoiding it in a simple formal way. The method uses a
geometric representation of the interface, the Gibbs construction, together with the assumption that while the internal state of the interfacial shell may be unknown it is fixed
by equilibrium with the bulk phases on either side.
7.6.1 The Gibbs construction
transition shell
dividing surface
...
Fig. 7.7:
The Gibbs model of an interface. The three-dimensional

transition shell is replaced by a two-dimensional surface.
The model that is used for the thermodynamics of surfaces is illustrated in Fig.
7.7. The figure shows two homogeneous phases separated by an interface. The transition
shell between the two phases is shaded, and includes the whole volume of material that is
perturbed by the interface. In the Gibbs construction the three-dimensional transition
shell is replaced by a hypothetical, two-dimensional dividing surface, which is placed so
that it is roughly coincident with the physical interface. The bounding phases are
imagined to extend homogeneously up to the dividing surface from either side. The
model system is then given a thermodynamic content that duplicates that of the actual
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transition shell by defining surface excess quantities of energy, entropy and mass that are
imputed to the dividing surface itself.
I
Let EI, SI and Nk be the actual quantities of energy, entropy and mole number of
the kth chemical species contained in a segment of the interfacial shell. Let the dividing
surface that replaces that segment have area, A, and let it divide the volume, V, of the
transition shell into subvolumes V and V, which lie on the and sides of the
interface, respectively. If the thermodynamic content of the model of the interfacial shell
is to reproduce the content of the actual shell, then the dividing surface must have surface
I
excesses of energy, ES, entropy, SS, and chemical content, Nk , such that
ES = EI - EV V - EV V
7.93
SS = SI - SV V - SV V
S
Nk = Nk - nk V - nk V
7.94
(k = 1,...,m)
7.95
where EV and SV are the energy and entropy per unit volume, nk is the molar density of
the kth component, and there are m chemical components in the system. The surface
excess quantities are said to be adsorbed on the surface. Their densities are twodimensional (quantity per unit area), and are given by
ES
ES = S
7.96
SS
SS = S
7.97
Nk
k = S
(k = 1,...,m)
7.98
7.6.2 The fundamental equation of an interface

Since the thermodynamic state of the transition region is given by its entropy,
chemical content and volume, the state of the surface can be characterized by the
adsorbed entropy and chemical species and the surface area. (As Gibbs showed, this is
true even when the surface is curved, if the dividing surface is placed properly at the
interface.) It follows that the fundamental equation for the interface can be written
ES = ES(SS, {NS}, A)
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By analogy to the energy function for a bulk phase, the partial derivatives of this function
with respect to entropy and chemical content define the temperature and chemical
potentials at the interface:
ES
SS = T
7.100
ES
NS = k
k
7.101
The change of energy with area defines the interfacial tension, :

ES
A =
7.102
The interfacial, or surface tension is the two-dimensional analog of the pressure, and is
the force that resists the extension of the surface. It is necessarily positive:
>0
7.103
since, if it were negative, the surface would grow spontaneously.

Since the adsorbed energy, entropy and chemical content of a homogeneous interface increase linearly with its area, the fundamental equation of the surface has the integrated form (cf. Sec. 7.5.4 above)
S
ES = TSS + A + kNk
7.104
7.6.3 The conditions of equilibrium at an interface

Since the interface can exchange energy and chemical species with either of the
adjacent phases, it can be easily shown that, when the system is in equilibrium, its
temperature, T, and chemical potentials, k (k = 1,...,m), are the same as those in the
surrounding phases. It follows that the bulk phases act as a thermochemical reservoir for
the interface, which is, effectively, an open system. The controllable variables are T, {}
and A, where the temperature and chemical potentials are controlled by setting their
values in the bulk phases, and A is the area of the interface.
As discussed in Sec. 7.4.3, the equilibrium of an open system requires that its
work function,
S
= E - TS - kNk
k
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have a minimum value for given values of T, V and the set {}. The work function of
the interface is
S
S = E - TSS - kNk
= A
7.106
Equation 7.54 shows that the surface tension is just the surface excess of the work
function per unit area, just as the pressure is the (negative) work function per unit volume
of the bulk. The general condition of equilibrium is, by analogy to eq. 7.54,
(S)T,{} = (A)T,{} 0
7.107
that is, the interface is in equilibrium only if every possible change in the state of the
interface that does not alter its temperature or chemical potentials increases S. The
possible changes in the interface are of two types: those that change the state of the
interface at fixed area (that is, those that change the internal state of the transition shell),
and those that change the area. Consider each of these in turn.
Changes in the internal state of the interface

If we fix the area, eq. 7.105 becomes
()T,{} 0
7.108
Hence, the equilibrium state of the interface is that which has the least value of for
given values of T and {}. If we were trying to compute the internal structure of the
interface, we would do that by comparing various possible structures and accepting that
which leads to the lowest value of .
It is useful to recognize that the condition 7.108 can be read in reverse: any
spontaneous change in the state of the interface must decrease its interfacial tension.
Many important interfacial phenomena can be easily understood on the basis of this
simple rule. For example, an impurity that is adsorbed onto a solid surface from the
atmosphere will remain on the surface if its presence decreases , but will be drawn into
the interior, or repelled back into the atmosphere, if it increases . An impurity in a
polygranular solid, such as sulfur in steel, will segregate to grain boundaries if it lowers
the interfacial tension of the boundary, but will otherwise remain in the bulk. Two solids
will spontaneously bond together only if their interfacial tension is less that the sum of
their surface tensions in air. We will encounter other examples later in the course.
Equilibrium at a curved interface

Next, consider changes in the shape of the interface at constant interfacial tension,
for example, when a curved interface is deformed or displaced. In the simplest example,
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the interface is spherical, and separates phases (call them and ) that have different
pressures (P and P), as illustrated in Fig. 7.8.
If the radius, R, of the interface changes, it also changes the volumes of the
bounding phases. The work function for the system shown in the figure is
= - PV - PV + A
7.109
When R is changed, infinitesimally, to R + R the change in is

= - (P - P)4R2R + (8R)R
2
= - 4R2(P - P) - R R
7.110
The change in can always be made negative, by choosing the sign of R, unless the
bracketed term vanishes. Hence the sphere is only in equilibrium with respect to
expansion or contraction of the interface if
2
(P - P) = R
7.111
Note that equilibrium is only possible if the pressure inside the sphere, P, is greater than
that outside, P. In the limit of a plane interface, R , the pressures are the same.
...
Fig. 7.8:
A sphere of phase , with pressure, P, and radius, R, enclosed

by a surface and embedded in phase with pressure P.
Equation 7.111 is a special case of a condition of mechanical equilibrium that applies to curved surfaces in general. Whatever the shape of a curved surface, it is always
possible to characterize its local curvature by measuring its radius of curvature along two
perpendicular axes that lie in the surface. Its mean curvature, K is related to these two
radii by the equation
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1
=R
1
+R
7.112
The condition for mechanical equilibrium across the interface is, then,
(P - P) = K
7.113
where P is the pressure in the interior, which is defined as the side of the interface that
contains the shortest radius of curvature. In the case of a sphere, K = 2/R, which regenerates eq. 7.111. In the case of a cylinder, K = 1/R, where R is the cylinder radius.
Equilibrium at a three-phase junction line

A two-phase interface cannot simply end; it either closes on itself, as it does in the
case of the sphere shown in Fig. 7.8, or terminates along a line where three interfaces
meet, as illustrated in Figs. 7.9 and 7.10. We distinguish two types of three-phase junction lines. In the first type, which is exemplified by the line around the periphery of a
drop of oil floating on water and by a three-grain junction line in a polygranular solid, all
three phases can change shape by growth or mechanical deformation. In this case the
three interfaces met at angles that are, ordinarily, not all that far from 120, as illustrated
in Fig. 7.9.
...
Fig. 7.9:
View perpendicular to a three-phase junction line where phases

, and meet.
In the second case, which is exemplified by a liquid droplet sitting on a solid surface, one of the phase is much more rigid than the other two, and the surface of that phase
continues straight through the junction line (Fig. 7.10).
To find the equilibrium configuration at a three-phase junction line it is simplest
to use a force balance, in which each interface is imagined to exert a perpendicular pull
on the junction line with a force per unit length equal to its surface tension, . The
justification for this approach is illustrated in Fig. 7.11, which shows an element of
surface that terminates in a junction line. If a unit length of the junction line is displaced
normal to itself, as shown in the figure, the work done is
W = S = A
7.114
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which is exactly equal to the work done by a force, , per unit length of junction line that
acts perpendicular to it. It follows that equilibrium can only be obtained at a junction line
if the three interfacial tensions are in balance.
Fig. 7.10: A liquid-like droplet () sitting on a rigid surface (). The periphery of the droplet is a three-phase junction line where the
and interfaces form the contact angle, .
In the case illustrated in Fig. 7.9, the force balance leads to an equation that is
known as the Neumann triangle of forces. If we define the vector force, ij , as a force
that has a magnitude equal to the interfacial tension of the ij interface, and a direction that
lies in the plane of the ij interface perpendicular to the three-phase junction line, then the
condition of equilibrium at the line illustrated in Fig. 7.9 is that
+ + = 0
7.115
When the three tensions are identical, as they are, for example, when the interfaces are
grain boundaries in a solid that is isotropic in its surface properties, then the equilibrium
condition is that the three interfaces make angles of 120 to one another.
dA
Fig. 7.11: Illustration of the action of the surface tension on a three-phase

junction line.
In the case illustrated in Fig. 7.10, the force balance leads to a relation that is
known as the Young equation. Since the substrate solid is rigid, we need only balance
forces parallel to the substrate surface. These forces are in balance if the interface
meets the surface at an angle, , the contact angle, that satisfies the relation
cos() =
7.116
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Of course, cos() must have a value that lies between -1 and 1. If the right-hand side of
eq. 7.116 is greater than 1 or less than -1, the equation has no solution. In the former case
the phase spreads over the surface to form a continuous film, and is said to wet the
surface. In the latter case, the phase is repelled by , and is separated from it by a thin
film of .
The macroscopic shape of a crystal

If a crystal grows in free contact with the atmosphere then it can take on any
shape it chooses. The preferred shape is that which minimizes the total surface energy
S = kAk
7.117
where k is the surface tension of the kth element of the external surface of the crystal,
Ak is its area, and the sum is taken over the whole external surface. Every crystal is at
least slightly anisotropic in its surface tension; close-packed or, in ionic crystals,
electrically neutral surface planes invariably have lower surface tension. On the other
hand, the total surface area is minimized if the crystal is a sphere, which uses all planes,
and increases as the crystal develops facets with preferred orientations.
The macroscopic shape of a crystal reflects the competition between the drive to
minimize area, which favors a spherical shape, and the drive to present low-tension surfaces, which favors a faceted shape. In most metallic and covalently bonded solids the
anisotropy in the surface tension is not great enough to drive a faceted shape. The
faceted "crystals" that form in nature are almost always strongly ionic materials whose
interfacial anisotropy is due to the fact that only certain planes are electrically neutral.
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Chapter 8: Simple Solids

Once out of nature I shall never take
My bodily form from any natural thing
But such a form as Grecian goldsmiths make
Of hammered gold and gold enamelling
- William Butler Yeats, "Sailing to Byzantium"
8.1 INTRODUCTION
While it is difficult to calculate the thermodynamic properties of solids with
numerical accuracy, it is relatively easy to develop a qualitative understanding of them.
For this purpose, it is useful to consider the three model solids: a perfect crystal, a random solid solution with near-neighbor bonding, and a slightly imperfect crystal.
First, we shall consider the perfect crystal. Its energy can be written as the sum of
three terms: the net binding energy at zero temperature, which is the binding energy when
the atoms are located at their equilibrium positions on the crystal lattice, the vibrational
energy, which is the energy of atom motion about the equilibrium positions, and the
electronic energy, which is the energy due to thermal excitations of the electrons. As we
have defined it, the binding energy depends only on the volume of the crystal. The vibrational and electronic energies increase with temperature. That increase, which is measured by the specific heat, CV, is primarily due to the thermal excitation of lattice vibrations. In most solids, the vibrational specific heat is governed by a material property, the
Debye temperature, D, which provides a rough measure of the energy required to excite
all possible lattice vibrations. In the low-temperature limit (T < D/4), the specific heat
increases with the cube of the temperature, Cv fi T3, essentially because more and more
lattice vibrational modes are excited as the temperature is raised. At high temperature, T
> D, the specific heat approaches a constant, Cv 3Nk, essentially because all possible
lattice vibrations are excited. The electrons also contribute to the specific heat since they
are also excited to higher energy levels as the temperature is raised. However, because of
the Pauli exclusion principle, only those electrons that are very close to the Fermi energy
can be excited. Since the number of such electrons is always small, their contribution to
Cv is negligible at ordinary temperatures.
Given the specific heat, it is possible to find the thermal contribution to the
Helmholtz free energy of a crystal, which establishes the form of the fundamental equation. Differentiating this equation leads to the entropy, and differentiating it again produces the compressibility and the coefficient of thermal expansion (as well as regenerating Cv). The entropy depends on the Debye temperature. The compressibility and coefficient of thermal expansion depend both on D and on its derivative with respect to
volume, which is specified by a material property known as the Gruneisen parameter, .
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Second, we shall consider a random solid solution. When the solid is a solution
with more than one chemical component, as are most of the materials of interest to us, its
free energy is affected by the configurational entropy that arises from the many different
ways in which distinct kinds of atoms can be arranged over the lattice sites. When all
configurations are equally likely, the configurational energy can be calculated as described in the previous chapter. We use it to compute the fundamental equation and explore the behavior of a simple solution, in which each atom is assumed to bond to its
nearest neighbors only. The model illustrates how the configurational entropy dominates
behavior when the temperature is sufficiently high, and produces mutual solubility between chemical species that would segregate apart (or form ordered compounds) at lower
temperature.
Finally, we shall consider an imperfect crystal and calculate the equilibrium density of defects as a function of temperature. The results show that the crystal always contains vacancies, whose concentration increases exponentially with the temperature.
However, the other, high-energy defects, such as dislocations and grain boundaries, are
non-equilibrium features that would seldom be found if an unconstrained equilibrium
were easily attained.
8.2 THE PERFECT CRYSTAL

Consider a perfect, crystalline solid that contains a given number of atoms (N) in
an essentially fixed volume (V), and whose temperature, T, is fixed by its environment.
As discussed in the previous chapter, the Helmholtz free energy of this solid can be found
by identifying all of its possible states, computing their energies, and using the results to
find the canonical partition function (eq. 7.91). This method is difficult, but it works for
any system. When the system is a single, perfect crystal. however, there is an easier way.
We need only calculate the mean value of the internal energy, E, of the material as a
function of temperature. The equation that relates the internal energy of a system to its
temperature, volume and particle (or mole) number is called the caloric equation of state:
E = E(T,V,N)
8.1
In the general case, the caloric equation of state is not equivalent to the fundamental equation. From the definition of the Helmholtz free energy,
F
E = F + TS = F - TT
F
TT
=-
T2
8.2
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Eq. 8.2 shows that the caloric equation of state is related to the partial derivative of
F(T,V,N) with respect to T. If there is a part of F that is linear in T (that is, an additive
term that has the form Tg(V,N), where g is a function of V and N only) this part is not determined by the caloric equation of state. To completely determine F we also need the
thermal equation of state,
F
P = P(T,V,N) = - V
8.3
to fix the volume dependence of F.

However, in the specific case of a perfect crystal, the fundamental equation does
not contain volume-dependent terms that divide out of 8.2. It follows that the fundamental equation of a perfect crystal, F(T,V,N), can be calculated from the caloric equation of
state.
To compute the internal energy of a perfect crystal we write it in the form
E = E0(V) + ED(V,T)
8.4
where we have left the dependence on the particle number, N, implicit (N is fixed).
E0(V) is the energy of the solid in the limit T = 0. It is essentially equal to the binding
energy of the solid when all atoms are in their static equilibrium positions and the electrons are in the lowest-energy electron states. (There is also a small zero-point vibrational energy which is a quantum-mechanical effect that makes a negligible contribution
to the energy at finite temperature). We discussed the binding energy in Chapter 3. In
this chapter we are concerned with the temperature-dependent part of the energy,
ED(V,T), the thermal energy.
There are two potentially significant contributions to the thermal energy: the vibration of atoms about their equilibrium positions, which become increasingly violent as
the temperature is raised, and the excitation of electrons, particularly the valence electrons that have energies near the Fermi level and can be excited to relatively high-energy
states. We consider these in turn, and will find that, except in the case of a metal at very
low temperature, almost all of the thermal energy is due to the atomic vibrations.
To appreciate the vibrational energy we need to understand the nature of lattice
vibrations in a solid.
8.2.2 Lattice vibrations
At finite temperature the atoms in a solid are in continuous thermal motion about
their equilibrium positions. To describe the vibration of an atom it is necessary to specify
its motion along each of the three perpendicular directions in space. Since an atom can
move at different velocities along the three directions in space, each atom has three viPage 187
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brational degrees of freedom. It follows that a solid that contains N atoms has 3N vibrational degrees of freedom, three for each atom.
However, the motions of the atoms in a solid are not independent of one another.
The atoms are coupled together by strong bonding forces. If a particular atom is displaced from its equilibrium position the lengths and angles of the bonds it makes with its
neighbors are changed. The resulting forces act both to restore the displaced atom to its
equilibrium position and to displace its neighbors to accommodate its displaced position.
The displaced neighbors, in turn, exert forces that tend to displace their neighbors. In this
way the displacement of an atom generates a vibrational wave that propagates through
the solid. These waves are called the normal modes of vibration of the solid. Since there
are a total of 3N vibrational degrees of freedom of the atoms, there are 3N normal modes.
Transverse vibration of a linear chain of atoms

A particular example of a displacement wave in a linear chain of atoms is shown
in Fig. 8.1. Each atom displaces its neighbor with the result that the vertical displacements of the atoms are described by a sinusoidal wave with wavelength, . The normal
vibrations include waves with all possible values of the wavelength, .
/2
a
Fig. 8.1: A transverse displacement wave of wavelength, , in a linear
chain of atoms.
To find all of the possible vibrational waves in a linear chain like that shown in
Fig. 8.1, let the chain have a total of N atoms, located at positions x = na, where n is an
integer. A transverse wave like that illustrated can be described mathematically by the
relation
ikx
u(x) = u0e
8.5
where u(x) is the vertical displacement of the atom at x = na and k is the wave vector,
2
k=
8.6
eik(x+) = eikx eik = eikx e2i = eikx
8.7
Since
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the displacement is periodic with period, .

The displacement waves that actually can appear in a finite chain of N atoms are
affected by end effects at the terminations of the chain. If N is large, these are surface effects that make a negligible contribution to the energy. To remove them we adopt what
are called periodic boundary conditions. We imagine the chain of N atoms to be embedded in an infinite chain that has the property that every N-atom segment is like every
other, in the sense that identically situated atoms in every segment have the same displacement. The displacement is then periodic with the macroscopic period, Na:
u(x + Na) = eik(x+Na) = u(x) = eikx
8.8
By an analysis like that used in eq. 8.7, equation 8.8 holds only if
kNa = 2m
8.9
where m is an integer. Hence the allowed values of the wave vector, k, are
2m
k = Na
8.10
There are exactly N independent values of the integer, m. To see this, let m = N + p,
where p is an integer. Then
2inp
eikx = eikna = expi2n + N
2inp
= exp N = eik'x
8.11
where k' = 2p/Na. Hence the waves that are generated by wave vectors for which m > N
simply repeat those for which m N. It is most convenient to chose the N values of m to
be the set
N
N
- 2 m 2
8.12
(there are only N independent values since - N/2 gives the same wave as N/2). With this
choice the N independent values of k are
-a <ka
8.13
and are symmetric about k = 0. The range given in 8.13 is called the first Brillouin zone
of the linear chain.
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The vibrational waves in a solid are not static. The displacement due to the kth
wave at any given atom oscillates with angular frequency, , so that the displacement of
the atom at position, x = na, at time, t, is given by the time-dependent function
u(x,t) = u0eikx e-it
8.14
The frequency, , increases with the magnitude of the wave vector, k. To see why this
should be so refer back to Fig. 8.1. The larger the value of k, the smaller the wavelength,
, and, hence, the larger the relative displacement between adjacent atoms in the chain.
The larger the displacement, the larger the force that acts on the displaced atom and,
hence, the greater the frequency of vibration. For this reason is an increasing function
of k. The function
= (k)
8.15
is called the dispersion relation for the lattice waves. The dispersion relation for a transverse vibration in a simple one-dimensional chain of atoms is plotted schematically in
Fig. 8.2.
- /a
Fig. 8.2:
0
k
/a
The dispersion relation, (k), between the wave vector and frequency for the transverse vibration of a one-dimensional chain
of atoms.
The ratio
(k)
c(k) = k
8.16
is the velocity of the wave. Using equation 8.16, the displacement imparted by the wave
can be written
u(x,t) = u0eik(x-ct)
8.17
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and hence propagates with the velocity, c. When the wave vector, k, is small the dispersion relation is linear:
= ck
8.18
The waves in a solid that have very long wave-lengths (small k) are sound waves, of the
type that might be made, for example, by striking the solid with a hammer. Hence the
constant velocity, c, is the speed of sound in the linear chain.
The transverse displacement of an atom, u(x,t), at a point, x = na, in the linear
chain at time, t, is the sum of the instantaneous displacements imposed by all of the vibrational waves that are excited. Hence,
u(x,t) = u0(k)ei[kx - (k)t]
8.19
While the behavior of the individual vibrational waves is simple and sinusoidal, the oscillation of an atom is the sum of many such waves, and may appear quite chaotic. It is for
that reason that it is simplest to visualize the thermal motion of the atom in terms of the
lattice waves, or normal modes of vibration.
Displacement waves in three dimensions

The extension of these concepts into the three-dimensional motion of atoms in
real crystals is relatively straightforward, but more difficult to visualize.
longitudinal
transverse (2)
- /a
0
k
/a
Fig. 8.3: Schematic drawing of the dispersion relation for a linear chain
of atoms that can move in three dimensions. The two transverse
vibrational modes have the same dispersion relation. Note the
higher sound speed for the longitudinal mode.
If the atoms of the linear chain vibrate in three dimensions we need two more sets
of waves to describe their motion. These can be taken to be a second set of transverse
waves that displace the atoms perpendicular to the plane of Fig. 8.1, and a set of longitu-
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dinal waves that displace the atoms toward one another along the line. The
displacements associated with each of these sets of waves are described by equations like
8.8, with wave numbers given by 8.10. The two transverse modes ordinarily have the
same dispersion relation. However, the longitudinal mode has a different dispersion
relation. The frequency of a longitudinal wave of given k is ordinarily greater than that of
a transverse wave since the atoms are displaced toward one another and, hence,
experience larger restoring forces. You may already be familiar with the fact that
longitudinal and transverse sound waves travel with different velocities through solids.
Fig. 8.3 is a schematic drawing of the dispersion relation of a linear chain of identical
atoms that move in three dimensions.
Lattice vibrations in a simple cubic crystal
The changes that result when the one-dimensional chain of atoms is replaced by a
three-dimensional crystal are easiest to see when the crystal has a primitive cell with a
simple cubic structure. A simple cubic crystal has linear chains of {100} planes of atoms
in three perpendicular directions. If we refer the crystal to a Cartesian coordinate system
with axes along the three edges of the cubic unit cell, then the wave numbers of the
vibrational waves are described by the wave vector
k = kxe x + kye y + kze z
8.20
where kx, ky, and kz are the wavenumbers of one-dimensional vibrational waves in the
coordinate directions specified by the perpendicular unit vectors, e x , e y and e z .
If the crystal contains N atoms (N unit cells since there is one atom/cell), then the
length of the crystal in each of the coordinate directions is N1/3a, where a is the edge
length of the unit cell. If periodic boundary conditions are imposed along the x, y and zaxes, the allowed values of kx, ky and kz are
2mi
ki = 1/3
N a
8.21
where i = x, y or z. There are N1/3 independent values of mi for each value of i (we can
always choose N such that N1/3 is an integer). If we let these be the values - N1/3/2 mi
N1/3/2, as in the one-dimensional case, then the independent values of ki are given by
- a ki a (i = x, y, z)
8.22
The independent wave vectors, k, are obtained by selecting distinguishable sets of

one-dimensional wave vectors {kx, ky, kz} in all of the ways that are permitted by eq.
8.22. Hence the total number of independent wave vectors is the product of the numbers
of values of kx, ky and kz, which is N, the total number of atoms. Since there are three
polarizations of the wave for every value of k (two perpendicular transverse waves and
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one longitudinal wave in the simplest case) the total number of independent waves is 3N,
equal to the total number of vibrational degrees of freedom of the N atoms.
a
-
a
-
a
-
a
Fig. 8.4: The first Brillouin zone of a simple cubic crystal, showing an
arbitrary wave vector, k, in the Brillouin zone.
The independent wave vectors, k, are confined to the three-dimensional Brillouin
zone shown in Fig. 8.4. The volume of the Brillouin zone is
=
(2)3
(2)3
=
vc
a3
8.23
where vc is the volume of the unit cell. The terminal points of the wave vectors, k, that
is, the points {kx, ky, kz}, are uniformly distributed through the Brillouin zone. Since
there are N wave vectors, and 3 vibrational states per vector, the independent vibrational
states (which are identified by the points {kx, ky, kz}) are homogeneously distributed
through the volume of the first Brillouin zone with the density
3Nvc
3N
3V
n0 = =
=
(2)3
(2)3
8.24
where V is the volume of the crystal.

The dispersion relation for the solid assigns a frequency, , to each wave vector,
k:
= (k)
8.25
The dispersion relation along any given line through the Brillouin zone qualitatively resembles that shown in Fig. 8.3, although, in the case of a three-dimensional crystal it may
be much more complicated, with peaks and valleys at intermediate values of k.
Moreover, the value of (k) varies with direction in the crystal. The vibrations may not
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be strictly longitudinal and transverse if the direction is not along one of the symmetry
axes, [100].
Vibrational modes in primitive crystal structures

When the solid is not a simple cubic crystal its vibrational behavior is more
complicated still. The simplest case is a one-component solid or random solid solution
with a primitive crystal lattice (atoms on the points of a Bravais lattice) that is not simple
cubic. The FCC and BCC metals and alloys are examples (HCP and diamond cubic materials are not since they have a minimum of two atoms per unit cell). In these solids the
repeat vectors for the atoms are the translation vectors of the primitive cell. As described
in Chapter 3, these vectors are not orthogonal. The consequence is that, while the wave
vector, k, can always be referred to cubic axes and written in the form given in eq. 8.20,
its components, kx, ky and kz are not given by the simple relation, 8.22, but by more
complicated relations that reflect the fact that the periodic boundary conditions are imposed along axes (the crystal axes of the primitive cell) that are not parallel to x, y and z
and are not orthogonal to one another. The result is that the first Brillouin zone is not a
cube, but a figure with a more complicated shape that depends on the particular lattice.
However, whatever the shape of the first Brillouin zone, it always contains exactly 3N vibrational states, and these are always homogeneously distributed with the
density n0 given by equation 8.24. Moreover, if the dispersion relations are measured
along a line through the Brillouin zone that passes through the origin, in the usual case
the curves are qualitatively similar to those drawn in Fig. 8.3.
Lattice vibrations in non-primitive structures

A different kind of complication intrudes when the crystal has more than one
atom in its smallest unit cell (the primitive cell of its Bravais lattice). Two kinds of crystalline solids have this property: one-component solids and solid solutions with nonprimitive lattices, such as the HCP and diamond cubic structure, and compound structures
in which each lattice site is occupied by a group of atoms, including interstitial compounds like NaCl and -ZnS, and ordered substitutional compounds like Cu3Au, where
the ordering of substitutional species on the atom sites changes the unit cell (in the case
of Cu3Au, from FCC to simple cubic with four atoms per simple cubic unit cell).
a
Fig. 8.5:
A linear diatomic chain of atoms vibrating in the optical

mode that corresponds to k = 0. The center of mass of each
unit cell remains fixed.
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In these solids a group of atoms sits at every site of the Bravais lattice. As a consequence, the vibrational states include two distinct kinds of vibrations: acoustic modes,
in which the atoms in the group associated with a given lattice point are displaced together, and optical modes, in which the different atoms in the atom group are displaced
with respect to one another. The optical modes are essentially vibrational states in which
the whole molecule is displaced according to a lattice wave with vector, k, while at the
same time the atoms in the molecular group vibrate with respect to one another. As an
example, the optical mode that corresponds to k = 0 in a diatomic linear chain is shown in
Fig. 8.5. The center of mass of the unit cell remains stationary (k = 0) while the two different atoms vibrate with respect to one another.
optical
acoustic
- /a
Fig. 8.6:
0
k
/a
Schematic drawing of the dispersion relation for a diatomic

linear chain like that shown in Fig. 8.5. There are 3 acoustic
modes and 3 optical modes: 2 transverse, with the same dispersion relations, and 1 longitudinal.
The dispersion relation of a diatomic linear chain like that shown in Fig. 8.5 is
drawn schematically in Fig. 8.6. The optical modes introduce three new dispersion relations, two for the transverse optical modes and one for the longitudinal optical mode, in
which the atoms in the molecules are displaced toward one another. The frequencies of
these modes are significantly higher than those of the acoustic modes, since nearestneighbor atoms are displaced. The number of vibrational states in each mode, acoustic or
optical, is equal to 3Nc, where Nc is the number of unit cells rather than the number of
atoms. There are three acoustic modes, and there are three optical modes for each additional atom in the unit cell. Hence the total number of vibrational states is 3N, as it
should be.
The angular frequency, , of the optical vibration varies much less strongly with
the wave vector, k, than in the acoustic mode. The variation is often so weak that it is a
good approximation to assign a single, constant frequency, opt , to each optical mode.
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8.2.3 The vibrational energy
Quantized energy of vibration; phonons

The quantum theory of the harmonic oscillator applies to lattice vibrations, since
each normal mode of vibration behaves like a harmonic oscillator with angular
frequency, . The quantum theory asserts that the amplitude and, hence, the vibrational
energy of a harmonic oscillator is quantized, and can only increase in discrete steps. The
energy of a harmonic oscillator takes the discrete values
E = (n + 1/2)
8.26
where n is an integer, = h/2, where h is Planck's constant, and the added factor 1/2 corresponds to the zero-point energy of the oscillator, a purely quantum effect. Equation
8.26 has a form that suggests that the harmonic oscillator defines a quantum state with an
energy that has an inherent energy /2 and can hold an arbitrary number of particles,
n. These particles are called phonons, and are the elementary quantized excitations of the
lattice vibrations. They define the number of elementary excitations that have been used
in making the wave.
The fact that phonons behave like particles should not be surprising. The lattice
vibrations are waves that propagate through the lattice, and it is a common feature of the
quantum theory that waves behave like particles, and vice versa. The phonons of lattice
vibration are very much like photons, which are the particles of light and other electromagnetic waves.
Thermal effects: Bose-Einstein statistics

The phonons of lattice vibration do not obey the Pauli exclusion principle. A vibrational wave can have an arbitrary amplitude and energy, which requires that an arbitrary number of phonons can be in the same state. Quantum particles that have this property are called Bosons, and they have a thermal behavior that is described by BoseEinstein statistics. In particular, the expected level of excitation, that is, the expected
number of phonons, n(,T), in a vibrational state with frequency, , at temperature, T,
is given by the relation
1
n(,T) = /kT
e
-1
8.27
This complex relation can be simplified in two limiting cases. First, when kT >> , that
is, when the temperature is very high or the frequency very low, we can use the expansion
/kT
~ 1 + kT
8.28
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to derive the approximate result

kT
n(,T) ~
(kT >> )
8.29
Second, when >> kT, that is, when the temperature is low or the frequency is very
high, e/kT >> 1 and
- /kT
n(,T) ~ e
8.30
The vibrational energy

The expected value of the total energy of the lattice vibrations in a solid can be
written
Ev(T,V,N) = (n(,T) + 1/2)
8.31
where the summation is taken over the allowed frequencies of the lattice vibrations. The
energy depends on N because the total number of lattice vibrations increases with N. It
depends on V because the dispersion relation, and hence the spectrum of frequencies, ,
depends on the volume of the unit cell (the edge length, a, in the case of a linear chain or
a simple cubic crystal). It depends on the temperature, T, through the Bose-Einstein formula that gives the expected number of phonons, n(,T).
The general solution of equation 8.31 is very difficult, and requires a detailed
knowledge of the Brillouin zone and the dispersion relations. However, there are two
cases in which the equation can be solved almost exactly without a detailed knowledge of
the dispersion relation: the high-temperature limit, where kT >> for every vibration,
and the low-temperature limit, where n(,T) 0 for all but the lowest-frequency acoustic modes. In most cases, the two limiting solutions can be fit together to provide a relatively simple picture of the vibrational energy, and, hence, the vibrational contribution to
the specific heat, at all temperatures. We focus on the specific heat, which is easily measured experimentally. Its prototypic behavior is characterized by a material property,
called the Debye temperature, D.
8.2.4 The vibrational contribution to the specific heat
The high-temperature limit: the Dulong-Petit Law

The vibrational energy in the high-temperature limit is found by substituting the
high-temperature expression for n(,T), eq. 8.29, into eq. 8.31. Since kT/ >> 1/2,
we can neglect the zero-point vibrations. The result is
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E(T,V,N) ~ kT = 3NkT
8.32
Differentiating eq. 8.32 with respect to the temperature gives the vibrational contribution
to the specific heat in the high-temperature limit:
(CV)v = 3Nk
8.33
Equation 8.33 is called the Dulong-Petit Law. It asserts that the specific heat of a solid
approaches a constant, 3Nk, at high temperature, where 3N is the total number of vibrational degrees of freedom.
Low temperature: the Debye interpolation formula

The vibrational energy can also be calculated in the low-temperature limit where
only the lowest-energy vibrational modes are activated. For solids that have primitive
unit cells the result can be extended to provide a reasonable approximation for the specific heat at all temperatures. This result was originally obtained by Peter Debye early in
this century, and is known as the Debye interpolation formula for the specific heat.
To formulate the model used by Debye note that the low-energy vibrational
modes are the long-wavelength acoustic modes for which = ck, where k = |k| is the
magnitude of the wave vector. For simplicity we ignore the difference between the sound
speed, c, for the longitudinal and transverse vibrations, or use an appropriate weighted
average of the two speeds. The low-energy waves that have a particular energy, , lie
on the surface of a sphere with radius k = /c in the first Brillouin zone (for example, in
Fig. 8.4). Since there are n0 states per unit volume in the Brillouin zone (eq. 8.24), the
number of vibrational states, g(k)dk, that have wave vectors, k, with magnitude between
k and k+dk, is equal to the number of states per unit volume, n0, times the differential
volume of the Brillouin zone between spheres of radii k and k+dk:
g(k)dk = n0(4k2)dk
2d
= 4n0 3 = g()d
c
8.34
where g()d is the number of states with energies between and (+d).
To solve for the vibrational energy in the low-temperature limit we use the fact
that the summation over frequencies in eq. 8.32 can be replaced by an integral according
to the rule
km
dkg(k)
dg()

0
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where km is the maximum value of k, and m is the maximum value of . Equation 8.32
then becomes
m
1
(n(,T) + ) g()d
Ev(V,N,T) =
2
0
n(,T)g()d
= E +
8.36
where E is the energy of the zero-point vibrations. It is independent of temperature, E =

E(V,N), and so does not affect the specific heat.
- /a
...
Fig. 8.7:
0
k
/a
The Debye approximation for a linear chain. The dispersion

relation is replaced by its long-wavelength form.
To solve this integral Debye approximated the dispersion relation of the solid by
assuming that all waves propagate with sound speed, that is, that
= ck
8.37
for all values of k. The approximation is illustrated in Fig. 8.7 for the case of a linear
chain of atoms. It is a good approximation for the low-energy modes, and hence should
provide a good estimate of the vibrational energy at low temperature, where only these
modes are activated, but becomes less accurate for the more energetic vibrations near the
edge of the Brillouin zone.
If all of the vibrations obeyed the dispersion relation given by eq. 8.37 then the
vibrational states would be located in a sphere centered around k = 0; the Brillouin zone
would be spherical. Since the total number of vibrational modes is 3N, the frequency of
the states at the outer boundary of the sphere, D, would satisfy the relation
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D
4n0
g()d =
3 2d
3N =
c
4n0
= 3 D3
3c
8.38
This equation defines the Debye cut-off frequency,

621/3
D = c v
8.39
where we have used equation 8.24 for n0; vc is the volume of the primitive unit cell.
The cut-off frequency, D, is used to define the Debye temperature,
c621/3
D = D/k = k v
8.40
where k is Boltzmann's constant. The Debye temperature is the temperature at which the
thermal energy, kT, becomes equal to the energy of a phonon with frequency, D, and is,
hence, a measure of the temperature at which all the vibrational states become activated.
When T > D, the high-temperature limit has certainly been reached.
If we substitute these approximations and results into equation 8.36, the vibrational energy is given by the integral
D
n(,T)g()d
Ev(T,V,N) = E +
0
4n0 D 3
/kT
= E + 3
d
c
e
-1
8.41
Now defining the integration variable,

x = /kT
8.42
and substituting the value of n0, we obtain, after a bit of algebra,
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3V(kT)4 xD x3
Ev(T,V,N) = E + 2
dx
2 (c)3 ex - 1
0
T 3 D x3
= E + 9NkT x
dx
e -1
D
8.43
where the limit of integration is

xD = D/T
8.44
Since the value of the integral depends on its upper limit, xD, equation 8.43 can be
written in the simpler form
Ev(T,V,N) = E(V,N) + 3NkTf(D/T)
8.45
where E is the zero-point vibrational energy and f(D/T) is a universal function (the
Debye function) of the variable D/T:
x
T 3 D x3
f(D/T) = 3 x
dx
e -1
D
8.46
The Debye function estimates the correction to the Dulong-Petit relation for the vibrational energy when the temperature is below D. Its value is always less than 1.
The specific heat at low temperature

In the limit of low temperature xD , and the Debye function can be found
analytically. The definite integral,
x3
4
x
dx = 15
e -1
8.47
so the vibrational energy is

4 T 3
Ev(T,V,N) = E(V,N) + 3NkT 5
D
8.48
The vibrational specific heat in the low-temperature limit is obtained by differentiating

equation 8.48 with respect to T, and is
CV =
4
4 T 3
3Nk 5
D
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8.49
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Fall, 2008
which differs from the Dulong-Petit law by the factor in braces. Equation 8.49 is exact in
the limit of low temperature, and shows that the vibrational specific heat of a solid varies
as T3 in the limit of low temperature.
CV
Fig. 8.8:
The vibrational specific heat in the Debye approximation.

For T > D/2 the specific heat is approximately constant, and
given by the Dulong-Petit Law.
The specific heat at finite temperature in the Debye model

The Debye function can be solved numerically to estimate the vibrational energy
and the specific heat for all temperatures. The result is important because it is universal.
In the Debye approximation the vibrational energy depends on only a single material parameter, the Debye temperature, D. In particular, the vibrational specific heat depends
only on the dimensionless combination, T/D. To see this we differentiate equation
8.43:
CV = T [Ev(T,V,N)]
D
= 3Nk{f(D/T) - T f'(D/T)}
8.50
where f'(D/T) is the derivative of f(D/T) with respect to its argument:

df(D/T)
f'(D,T) = d( /T)
D
8.51
Eq. 8.50 shows that, to within the accuracy of the Debye approximation, the vibrational
specific heats of all simple solids should have the same form when expressed as a function of the dimensionless temperature, T/D. This universal function is shown in Fig.
8.8. It is reasonably well obeyed by all solids that have primitive unit cells.
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Solids with non-primitive unit cells

Strictly speaking, the Debye model is restricted to solids that have only acoustic
vibrational modes, that is, to solids that have primitive unit cells such as FCC and BCC
solids. It can be extended to solids with non-primitive cells by accounting for optical
modes of vibration. It is often possible to do this to a reasonable approximation by assigning a single frequency to all of the optical modes. In any case, the Debye T3 law
governs the vibrational specific heat at very low temperature, since only the acoustic
modes are activated when T is small. We can simply define a value for D for solids
with non-primitive structures, such as diamond and the HCP metals, by fitting equation
7.126 to the low-temperature specific heat.
With this approximation the Debye model can be applied to crystals with nonprimitive structures, and works reasonably well for elemental solids, solid solutions and
ordered substitutional compounds. The model is less useful for interstitial compounds
and molecular solids, since the optical modes in these solids often have high frequencies.
The same approximation can be used to define the Debye temperatures of amorphous
solids, and works reasonably well for amorphous metals, semiconductors and simple
glasses. It is less useful for polymeric and other molecular glasses.
The Debye temperature as a material property

Given that the Debye temperature characterizes the vibrational specific heat of a
solid it is useful to see how it can be related to other material properties. According to
equation 7.117, the only material property on which it depends is the mean speed of
sound, the mean velocity of propagation of waves of long wavelength. The speed of
sound can be calculated from the elastic constants of the material, which we shall discuss
later, but can also be related to the strength of bonding in the solid. The stronger the
bonds, the stronger the force that tends to restore a displaced atom to its equilibrium position, and, hence, the higher the frequency and velocity of a sound wave. Hence strongly
bonded solids have high Debye temperatures (diamond has D 2000K), while weakly
bonded solids have low values (Pb has D 95K). For most metals, D lies in the range
200-500K.
8.2.5 A qualitative version of the Debye model
As the theoretical models of solid state physics go, the Debye model is a
relatively simple one. Nonetheless, it involves some rather messy integrals whose form
obscures the qualitative features of the physics that govern the lattice contribution to the
specific heat. For that reason, it is useful to describe an even simpler model that may
help to clarify the physics of the problem. While it is seriously deficient in mathematical
rigor, it does give the right functional dependence of the specific heat.
Following Debye, let us assume that the frequency of a lattice vibration is linearly
related to its wave number, = ck, as in eq. 8.37. At temperature, T, the lattice vibrations can be divided into two sets: those for which the phonon energy, , is small comPage 203
Materials Science
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pared to kT, and those for which it is large compared to kT. The former, low-energy vibrational modes are strongly excited, while the latter are not. Let T be the cut-off frequency that divides strongly excited vibrations from weakly excited ones, as illustrated in
Fig. 8.9. A crude representation of the Bose-Einstein function suggests that T 2kT is
a reasonable choice.
D
0
k
- /a
...
Fig. 8.9:
/a
Schematic drawing illustrating the division between excited

modes ( < T) and quiescent modes at temperature T.
Now make the approximation that all vibrations with < T are excited into the
high-temperature limit, with energy kT, while those with > T remain quiet. Since
D = kD, and since the 3N vibrational modes are spherically distributed through the
Brillouin zone, the number of excited modes is
3N 2T 3
D
N(T) ~
3N
T<D/2
8.52
T>D/2
the vibrational energy is
3NkT 2T 3
D
E(T) ~
3NKT
T<D/2
8.53
T>D/2
and the specific heat is
12Nk 2T 3
D
Cv(T) ~
3Nk
T<D/2
T>D/2
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The vibrational energy and specific heat given by eqs. 8.53 and 8.54 are in reasonable
numerical agreement with those predicted by the Debye model, and have the right temperature dependence in both the high-T and low-T limits.
A useful qualitative feature of this model is that it makes it clear why the specific
heat changes with temperature. At high temperature all of the available vibrational
modes are strongly activated. Increasing the temperature further raises the level of activation of each of the 3N modes by the same amount, so the specific heat is constant. At
low temperature, however, only some of the modes are strongly activated. Increasing the
temperature raises the energy in two ways: the energy of the activated modes is raised,
and vibrational modes that were previously quiet are activated. In this case the temperature increases both the energy per mode and the effective number of modes. As a consequence, the specific heat is a string function of the temperature.
8.2.6 The electronic contribution to the specific heat
The second contribution to the thermal energy of a perfect crystal is made by the
valence electrons, which reconfigure into excited states above the Fermi energy, EF, as
the temperature rises. There are Nz electrons, where N is the number of atoms and z is
the valence. Since these are in rapid motion through the crystal lattice one might expect
them to make a large contribution to the specific heat. However, they do not. The electronic specific heat is very small at all realistic temperatures, even in metals with high
electrical conductivity. The reason is that only a few of the valence electrons are excited
by an increase in temperature.
CV
B
T
A
T2
Fig. 8.10:
Plot of CV/T against T2. The slope gives the coefficient of

the vibrational contribution; the intercept is the coefficient of
the electronic term.
On the other hand, the electronic contribution to the thermal energy is responsible
for an anomalous feature of the specific heats of metals at very low temperature. In the
limit of low temperature the specific heat of a metal obeys an equation of the form
CV = AT + BT3
8.55
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where A and B are constants. The T3 term is due to lattice vibrations. While A is much
smaller than B, at temperatures so low that T >> T3 the linear term dominates. If one
plots the specific heat of a metal in the manner shown in Fig. 7.14, as CV/T against T2,
then the result is a straight line with slope, B, and asymptote, A.
The behavior of the electronic specific heat has its source in the Pauli exclusion
principle, which requires that there be only one electron in each permissible state.
Quantum particles that obey the Pauli exclusion principle are called Fermions. At finite
temperature they are distributed over the set of states available to them according to the
Fermi-Dirac distribution function, which states that the expected number of particles,
n(E), in a state with energy, E, at temperature, T is
1
n(E) = (E-EF)/kT
e
+1
8.56
where EF is the Fermi energy. Note that n(E) is always less than 1, as required by the
Pauli exclusion principle. The Fermi energy is the energy at which the probability that a
state is occupied is exactly 1/2:
1
n(EF) = 2
8.57
In the limit T 0 the exponential in the denominator of eq. 8.57 vanishes if E <
EF, and is arbitrarily large if E > EF. It follows that
1
limT0[n(E)] =
0
E < EF
E > EF
8.58
As we assumed in Chapter 2, all states below EF are filled in the ground state of the solid
(T 0) while all states above EF are empty. The Fermi level, EF, itself lies half-way between the highest filled and lowest empty states. In a metal the allowed electron states
are so close together at EF that the Fermi energy is essentially equal to the energy of the
highest filled state. In an intrinsic semiconductor or insulator the highest filled state lies
at the top of the valence band while the lowest empty state is at the bottom of the conduction band; EF is in the center of the band gap.
The Fermi-Dirac distribution function is plotted for some finite T in Fig. 8.11. In
the limit T 0 all states below EF are filled, all states above EF are empty. At finite
temperature the distribution differs significantly from the low temperature limit only for
states whose energies differ from EF by no more than the thermal energy, kT. When EEF > kT,
- (E-EF)/kT
n(E) e
Page 206
(E-EF > kT)
8.59
Materials Science
Fall, 2008
and rapidly asymptotes to 0 as the energy increases. When EF-E > kT,
(E-EF)/kT
n(E) 1 - e
(EF -E > kT)
8.60
and asymptotes rapidly to 1 as the energy falls below EF. [To derive equation 8.60 note
that (1 + x)-1 1 - x when x is small.]
EF
kT
n(E)
.5
0
E
...
Fig. 8.11:
The Fermi-Dirac distribution function for electrons at finite

temperature. Note that the difference from the ground state is
essentially confined to the shaded band of energies within kT
of EF.
The electronic specific heat of a metal

In a metal the Fermi energy lies within a band of allowed electron states. As the
temperature increases the electron distribution is smeared over the states within a distance, kT, of EF as shown in Fig. 8.11. Since the widths of bands of electron states are of
the order of several electron volts (eV), and 1 eV is the value of the thermal energy at
nearly 104K, only a very small fraction of the electrons within the valence band of the
metal are affected.
The thermal contribution to the electron energy can be roughly estimated in the
following way. Let Ng(EF)dE be the electron density of states at the Fermi level, the
number of electron states with energies between EF and EF+dE. The factor g(EF) is the
density of states per atom, and is a small number since there are only 1-4 valence electrons per atom. Assuming that g(EF) is approximately constant for a range of width kT
on either side of EF, then the total number of electrons that are excited at temperature, T,
is approximately
NkT
Ne(T) 2 [g(EF)]
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8.61
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where we have also assumed that 1/2 of the available electrons are excited. Each of these
electrons acquires a thermal energy of the order of kT. Hence the thermal contribution to
the electron energy is, approximately,
Ee(T)
N[g(EF)]
(kT) 2
2
8.62
EF
kT
n(E)
.5
valence
band
conduction
band
EG
0
E
...
Fig. 8.12: Fermi-Dirac distribution for a narrow-gap semiconductor at
moderate temperature.
It follows from eq. 8.62 that the electronic specific heat is of the form suggested
by eq. 8.55:
(CV)e = AT
8.63
where the coefficient, A, is

A Nk2[g(EF)]
8.64
A much more rigorous theoretical calculation [J. Ziman, Principles of the Theory of
Solids, p. 144] gives the result
2
A = 3 Nk2[g(EF)]
8.65
which shows that the simple model is not so bad.

The coefficient, A, is a small number. At ordinary temperatures the electronic
term accounts for only about 1% of the value of the specific heat. The electronic contribution is only observable at very low temperatures, where T >> T3. The electronic contribution to the thermal energy is otherwise negligible, and is not ordinarily included in
calculations of the fundamental equation of solids.
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Semiconductors and insulators

The electronic contribution to the specific heat of a semiconductor or insulator is
significantly smaller than in a metal. The reason is shown schematically in Fig. 8.12, in
which the Fermi-Dirac distribution is plotted against the distribution of allowed states in
an intrinsic semiconductor or insulator. The Fermi energy is located within the energy
gap. The magnitude of kT is less than .1eV at normal temperatures. The band gaps of
typical semiconductors are of the order of an electron volt while the band gaps of insulators are several eV. Hence very few electrons are excited across the band gap at finite
temperature, and the electronic specific heat is negligible.
We can find the Helmholtz free energy of the perfect crystal by integrating the
differential expression given in eq. 7.82:
F
TT
E=-
T2
8.2
Since eq. 8.2 is a partial differential equation in which the partial differential is taken at
constant volume, it actually determines F/T only to within an additive function of volume. However, in the case of the simple vibrating solid we are considering here no such
additive function appears (a fact that can be proved by invoking the Third Law of thermodynamics).
The low-temperature form of the fundamental equation

Equation 8.2 is easily solved in the low-temperature limit. Using eq. 8.48,
F
E 32Nk 2
=
T
TT
T2 5D3
8.66
4

F(T,V,N) = E(V,N) - NkT T 3
D
5
8.67
whose solution is
The Debye temperature, D, is a function of the volume per atom, since expanding the
solid changes the strength of binding between the atoms and, hence, changes the vibrational frequencies. Hence the right-hand side of eq. 8.67 is a function of T, V and N.
Since these are the natural variables for the Helmholtz free energy, eq. 8.67 is the lowtemperature form of the fundamental equation of a simple solid.
The entropy of the solid at low temperature is the vibrational entropy
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F
T 3
44
S = - T = 5 Nk
D
8.68
The pressure; the Gruneisen equation of state

The pressure of the solid is given as a function of (T,V,N) by the partial derivative
F
1 dD
E 34
P = - V = - V - 5 NkT4 4 dV
D
T 3 1 dln(D)
E 34
= - V - 5 NkT V dln(V)
D
8.69
where dln(x) = dx/x. The Debye temperature depends on the volume through the atomic
volume, v = V/N; the vibrational spectrum of the solid does not change if we simply increase the size of the solid by adding atoms at constant atomic volume. Since the partial
derivative in eq. 8.69 is taken at constant N, dln(V) = dln(v). If we now define the
Gruneisen parameter
dln(D)
V D
= - dln(v) = - V
D
8.70
which specifies the volume dependence of the Debye temperature, the pressure is given
by
T 3 1 dln(D)
E 34
P = P(N,V,T) = - V - 5 NkT V dln(v)
D
ED
E
= - V + V
8.71
where ED is the vibrational energy.

It can be shown that equation 8.71 holds at all temperatures for solids whose specific heats are well represented by the Debye interpolation formula. Equation 8.71 is
called the Gruneisen equation of state of a solid, and is obeyed reasonably well by all
simple solids, including simple compounds. The Gruneisen parameter, , is a dimensionless constant whose value lies in the range 1-3 for elemental solids, solutions and compounds that have simple crystal structures.
The two terms that contribute to the pressure represent two different physical processes. The first term contains the effect of the interatomic bonding. The binding energy
has a minimum at V0, the volume of the solid in the limit of zero pressure and temperature. If the solid is compressed to V < V0 the bonding term exerts a positive pressure
Page 210
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that tends to expand it to restore V0. If the solid is expanded to V > V0 the solid tends to
contract, and the bonding contribution to the pressure is negative. The second term includes the effect of the lattice vibrations. It is always positive. The lattice vibrations tend
to push the atoms apart.
8.2.8 Thermodynamic properties
Given the fundamental equation, we can also find the thermodynamic properties
of the solid. We have already discussed the specific heat, CV. The isothermal compressibility was defined in Chapter 7, and is:
1 V
T = - V P
T,{N}
8.72
Its reciprocal (the bulk modulus) is obtained by differentiating the Gruneisen equation of
state with respect to V. Assuming that is constant, the low-temperature result is
P
(T)-1 = - VV
T,{N}
2E
ED
ED
= V 2
+ V - V
V {N}
T,{N}
2E
ED
= V 2
- V [3 - 1]
V {N}
r0
(r)
Fig. 8.13:
8.73
change of equilibrium
radius with vibration
vibrational
energy states
.
The binding potential of a diatomic molecule, showing the
vibrational energy states and the increase of the equilibrium
radius as the vibrational energy increases.
The first term on the right in 8.73 is the bulk modulus at zero T, which is determined by the interatomic binding. The second term is much smaller in magnitude and is
due to the lattice vibrations. Since 3 > 1, the vibrational term decreases (T)-1, and
hence decreases the bulk modulus. The physical reason for this behavior is that, since
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is positive, an increase in volume decreases the Debye temperature, D, and hence

increases the vibrational energy, which is proportional to [D]-3. In effect, the binding
strength, which provides the spring constant for the lattice vibrations, goes down. This
has the result that the solid contracts more for a given increase in the pressure than it
would at T = 0. Hence the compressibility increases with the temperature.
The coefficient of thermal expansion is (Chapter 7):
1 V
T = V T
P,{N}
8.74
It can be shown that

P
1 V
1 V

V T P,{N} = - V P V,{N}TV,{N}
P
= TT
V,{N}
8.75
By differentiating the Gruneisen equation of state (8.71) with respect to the temperature
we find
P
CV

TV,{N} = V
8.76
CVT
V
8.77
and, hence,
T =
Equation 8.77 is known as the Gruneisen relation. Its validity is not confined to low temperature; it applies whenever the Gruneisen equation of state is valid.
The physical source of the coefficient of thermal expansion lies in the anharmonicity of the atom vibrations in the solid. To visualize this consider a diatomic
molecule, as we did in Chapter 2. The binding potential of the molecule, (r), has the
form shown in Fig. 8.13. The vibrations of the molecule have quantized values that are
indicated by the horizontal lines within the potential well. Because of the anharmonic
shape of the binding potential, the restoring force on the atoms is smaller when r > r0 than
it is when r < r0, and, hence, the atoms spend a greater fraction of the time at r > r0. This
has the consequence that the time average interatomic separation, r0(T), increases as the
vibrational energy increases, as shown in the figure.
The situation in a vibrating solid is qualitatively the same. The total binding potential between atoms is anharmonic, roughly as shown in the figure. As the vibrational
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energy increases the time average of the interatomic separation increases, so the solid expands.
8.3 THE RANDOM SOLID SOLUTION

8.3.1 The Bragg-Williams model
The previous section showed how the fundamental equation of a perfect crystal
could be found by considering its binding energy at zero temperature together with the
changes in its energy due to vibrational and electronic excitations as the temperature is
raised. In this section we formulate the fundamental equation of a random solid solution,
so that we can gain some insight into the influence of composition on the thermochemical
properties of solid solutions. To do this, we shall use a model called the Bragg-Williams
model, which is the simplest model of a solid solution that includes compositional
effects.
The Bragg-Williams model treats a binary solution of two kinds of atoms, A and
B, that are distributed over the sites of the fixed crystal lattice.. It assumes that the internal energy of the solution is equal to its binding energy, and assumes that E is independent of temperature (we discussed the thermal contribution to the energy in the previous
Section, and can add it to the model later, if we wish). To evaluate the binding energy, it
assumes that each atom interacts only with the atoms that are closest to it on the crystal
lattice. Since the energy is independent of temperature, the entropy is just the configurational entropy of the solution (Section 7.2.3), and is also independent of temperature.
The free energy of the solution is, then,
F(T,{N}) = E({N}) - TS({N})
8.78
where E is the binding energy at the equilibrium volume, V0, and S is the configurational entropy of the distribution of atoms over the atom sites of the solid solution. Both
E and S depend on the composition.
VAB
VAA
=A
=B
V BB
...
Fig. 8.14: Solution of A and B atoms, illustrating AA, BB and AB bonds.
To evaluate E, let each atom interact only with those atoms that are nearest
neighbors to it, as illustrated in Fig. 8.14, and assume that the bonding interaction is inde-
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pendent of temperature and concentration. The atom fraction of component B is x

=NB/N, where NB is the number of B-atoms and N is the total number of atoms (equal to
the total number of lattice sites). The atom fraction of A is (1-x).
If VAA is the energy of a bond between A atoms, VBB the energy of a B-B bond,
and VAB the energy of an A-B bond then the energy of the solution is
E = VAANAA + VBBNBB + VABNAB
8.79
where Nij is the number of nearest neighbor bonds of type ij (= AA, BB or AB). Let each
atom have z nearest neighbors. If the solution is random, the probability that an atom site
is occupied by a B-atom is x, the atom fraction of B, while the probability that it contains
an A-atom is (1-x). Hence each A atom has, in the mean, z(1-x) AA bonds and zx AB
bonds, while each B atoms has z(1-x) AB bonds and zx BB bonds. The total energy is,
then
1
E = 2 {NAz[(1-x)VAA + xVAB] + NBz[(1-x)VAB + xVBB]}
8.80
where NA is the number of A atoms, NB is the number of B atoms, and the factor 1/2 is
included because each bond is counted twice in the expression in braces. Since the number of A-atoms, NA = (1-x)N and NB = xN, equation 8.80 can be re-written:
Nz
E = 2 {(1-x)2VAA + x2 VBB + 2x(1-x)VAB}
Nz
1
= 2 (1-x)VAA + xVBB + 2x(1-x)VAB - 2(VAA + VBB)
Nz
= 2 {(1-x)VAA + xVBB + 2x(1-x)V}
8.81
where V is the relative binding energy

1
V = VAB - 2(VAA + VBB)
8.82
The relative binding energy, V, has a simple physical meaning: it is the difference
between the energy of an AB bond and the average of the energies of AA and BB bonds.
If V is positive the energy of the system is decreased if 2 AB bonds are replaced by an
AA bond and a BB bond, that is, if A atoms and B atoms associate preferentially with
one another. In this case the energy of the system is lowered if it decomposes into A-rich
and B-rich solutions. If V is negative, on the other hand, the energy is decreased if AA
and BB bonds are replaced by AB bonds, and we should expect the system to prefer a
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solid solution that eventually orders into an AB-type compound. The energy of the
random solution is graphed in Fig. 8.15 for the cases V > 0, V < 0 and V = 0.
V>0
E
VAA
V=0
V BB
V<0
...
Fig. 8.15: The binding energy of a random solution with near neighbor
interactions for three values of the relative binding energy.
8.3.3 The configurational entropy
To complete the calculation of the free energy we require the value of the entropy.
In this model we assume that only the configurational entropy is important. The configurational entropy of the random solution is given as a function of the composition, x, by
equation 7.20 of the previous chapter:
Sc = - kN[x ln(x) + (1-x) ln(1-x)]
8.83
The configurational entropy is plotted as a function of x in Fig. 8.16.
...
Fig. 8.16: The configurational entropy of a random solution as a function
of composition.
Note that the configurational entropy is well behaved in the limits x 0 and x
1; the function x ln(x) 0 in the limits x 0 or 1. However, the compositional derivative of the configurational entropy
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dS
dx = - kN[ln(x) - ln(1-x)]
8.84
is singular at both limits. It explodes to as x 0 and to - as x 1.

8.3.4 The free energy and thermodynamic behavior
The free energy of the random solution is obtained by summing the energy and
entropy:
F = F(T,V,{N}) = E - TS
Nz
= 2 {(1-x)VAA + xVBB + 2x(1-x)V} + NkT[x ln(x) + (1-x) ln(1-x)]}
8.85
Both the configurational energy and entropy are independent of the temperature. The
temperature enters the expression through its multiplication of the configurational entropy.
Unlike-atom attraction; low-temperature order

The thermodynamic behavior that is predicted by eq. 8.85 depends on the sign of
the relative binding energy, V. If V 0 then the free energy is negative and concave
(curved upward) at all values of x and T. As we shall see in the next chapter, the concavity of the fundamental equation has the consequence that the random solid solution is at
least metastable at all compositions and temperatures, and, therefore, can exist at all x
and T.
However, it does not follow that the random solid solution is the preferred configuration for all x and T. If V < 0 and T is low, the solution can lower its free energy by
forming an ordered arrangement that maximizes the number of AB bonds.
As a simple example, let x = 0.5, and assume that the crystal has a BCC structure
(z = 8), so that it is possible to arrange the atoms in a CsCl pattern with A atoms at the
cell centers and B atoms at the corners. In the ordered state, all bonds are AB bonds, and
the energy is
Eorder = 4NVAB
8.86
However, the configurational entropy (Sord) is zero. In the disordered state the energy is
1
Edis = 2NVAB + 2(VAA + VBB)
while the configurational entropy is
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Sdis = Nkln(2)
8.88
Since Sdis > Sord, the random solution has the lower free energy when T is large, and is
thermodynamically preferred. However, since Eord < Edis, there is a temperature low
enough that the ordered state has the lower free energy. It follows that the random solid
solution becomes at least metastable with respect to the ordered phase as the temperature
is lowered. This is precisely the behavior observed in -brass (CuZn). It is a solid solution with a BCC structure at high T, but an ordered compound with the CsCl structure at
low T.
While eqs. 8.86-8.88 are written for a specific case, the qualitative result is general. When V< 0 the random solid solution is always at least metastable with respect to
transformation into an ordered phase (or mixture of ordered phases) at sufficiently low
temperature. This result is in keeping with the Third Law of thermodynamics; when the
temperature is very small the equilibrium state of a multicomponent solid is always an
ordered structure or mixture of ordered structures.
Like-atom attraction; low-temperature decomposition

If V > 0, then the energy is a convex function of x while the entropy term, -Ts, is
concave. The behavior of the free energy per atom f(x) (= F(x)/N) is plotted in Fig. 8.17
for three values of the temperature. At high temperature the entropy dominates and the
function f(x) is concave; the system is a random solid solution at all compositions. At
low temperature the energy dominates the behavior of f(x) at intermediate values of x
but, because of the singularity in its compositional derivative, the entropy still dominates
in the limits x 0 or 1. Hence f(x) is a concave function near x = 0 and x = 1, but is
convex (curved downward) at intermediate values of the composition.
T3
VBB
VAA
f
T2
T1
A
...
Fig. 8.17: Free energy curves for a random solution with V > 0 at three
temperatures, T1 > T2 > T3.
As we shall see in the following chapter, a solid solution cannot exist when its
free energy function, f(x), is a concave function of x. If we try to mix equal concentrations of two components so that x = 0.5 at temperature T2 or T3 in Fig. 8.17, we will discover that we cannot do so; the solution will spontaneously decompose into a mixture of
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two solutions with different concentrations, one A-rich (x < 0.5) and one B-rich (x > 0.5).
We say that the A-B solution has a miscibility gap. We can form a solid solution at all
compositions at high temperature where the configurational entropy dominates the free
energy, but, if V > 0, cannot make a solid solution at intermediate compositions at low
temperature where the energy dominates.
Note, however, that the singularity in the slope of the free energy at x = 0 and 1,
which is due to the singularity in the slope of the configurational entropy, has the consequence that the free energy function is always concave when x is close to 0 or 1. This is
true no matter how high V may be, that is, no matter how much the species A and B dislike one another chemically. As we shall see in the following Chapter, this has the consequence that there is always some solubility for A in B and B in A. If the solution decomposes, it does not decompose into pure A and pure B, but into two solid solutions,
one of which is predominantly A with some B in solution, and the other predominantly B
with some A in solution. This is one example of the general thermodynamic principle
that everything is at least slightly soluble in everything else.
8.4 EQUILIBRIUM DEFECT CONCENTRATIONS

All real crystals are defective. They not only contain impurities in solution, but
are filled with internal defects, including vacancies and interstitialcies, dislocations, and
grain boundaries. It is important to recognize that vacancies, and, to a much lesser
extent, interstitialcies, are inherent defects that are present in finite concentration in the
equilibrium state of the crystal. They can be created or destroyed by processes that occur
spontaneously within the solid. Moreover, there are active mechanisms in the solid that
maintain the vacancy concentration at near-equilibrium values. Other crystal defects,
such as dislocations and grain boundaries, have very high formation energies and essentially zero concentrations in the equilibrium state. They are non-equilibrium defects that
are created during processing, and preserved because of the slow kinetics of the mechanisms that eliminate them.
To establish this, we compute the equilibrium concentration of defects in an otherwise perfect crystal.
8.4.1 The equilibrium vacancy concentration
When a crystalline solid is held at fixed temperature and pressure its equilibria are
controlled by the Gibbs free energy. The addition of a single vacancy to a crystalline
solid increases its Gibbs free energy by the amount
gv = ev + Pvv - Tsv
8.89
where ev is the formation energy of the vacancy, vv is the associated volume increase,
and sv is the entropy change which, in the case of an isolated vacancy, is due to the
change in the vibrational and electronic entropies of the atoms in the neighborhood of the
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vacancy. In most crystalline solids it is reasonable to neglect the volume and entropy increment for the addition of a single vacancy, in which case
gv ev
8.90
Let there be n vacancies in the solid, where n is sufficiently small compared to the
number of atoms, N, that the vacancies do not interact significantly with one another.
The free energy increment due to the vacancies is, then,
G = ngv - kT ln()
nev - kT[(N+n) ln(N+n) - n ln(n) - N ln(N)]
8.91
where the second term on the right-hand side is the configurational entropy, which we
have evaluated with the help of eq. 7.20. N+n is the total number of lattice sites; since
the number of atoms is conserved, the number of lattice sites in the solid changes when
vacancies are added. The equilibrium number of vacancies (ne) minimizes the Gibbs free
energy. Differentiating eq. 8.91 and setting the derivative equal to zero yields the condition:
d(G)
dn n = n = 0 = ev - kT[ln(N+n) - ln(n)]
e
8.92
The solution is
ne
e
N+ne = xv
ev
= e kT
8.93
where xv is the equilibrium concentration of vacancies, the fraction of lattice sties that
are vacant in the equilibrium state. [Note that the left-hand side of eq. 8.92 is the
definition of the chemical potential of a vacancy, regarded as a chemical species that
occupies atomic positions in the crystal. Eq. 8.92 shows that, in equilibrium, the
chemical potential of a lattice vacancy is zero. This is true because the number of
vacancies is not conserved. Vacancies can be created and destroyed, so their
concentration adjusts to minimize G.]
...
Fig. 8.18: Illustration of the creation or annihilation of vacancies by exchange with adsorbed atoms at an interface.
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While the vacancy concentration in a typical crystalline solid at moderate temperature is not large, it can be significant. The energy to form a vacancy, ev, is of the order
of 1 eV (electron volt) in a typical solid. An electron volt corresponds to the value of kT
at about 104 K. Hence the vacancy concentration in a typical solid at 1000 K ( 700 C)
is on the order 10-4, giving about 1018 vacancies per cm3 of crystal. The equilibrium vacancy concentration drops exponentially as the temperature decreases.
At moderate temperature most solids maintain vacancy concentrations that are
close to the equilibrium value. The reason is that defects within the solid act as sources
and sinks for vacancies, which are reasonably mobile at moderate temperature. Efficient
sources and sinks for vacancies include free surfaces, which can add or subtract vacancies
by adjusting the number of adsorbed atoms (as illustrated in Fig. 8.18), grain boundaries,
which can absorb or emit vacancies by reconfiguring the atoms in the boundary, and dislocations, which absorb or emit vacancies during climb, as discussed in Chapter 4.
At low temperature the vacancy mobility decreases dramatically. When a solid is
quenched from high temperature the vacancy concentration is frozen in for some time
after the quench. This behavior affects atomic diffusion in the solid, as we shall discuss
in the next chapter. It is also very important in the processing of semiconductor crystals
such as silicon. Vacancies are electrically active defects in a semiconductor and must be
held to a low concentration so that they do not alter its electrical properties. Hence, after
silicon crystals are processed at high temperature they are cooled slowly to achieve an
equilibrium vacancy concentration at a temperature where the vacancy concentration has
an acceptably small value before cooling to room temperature where Si vacancies are
nearly immobile.
8.4.2 Dislocations and grain boundaries
It is possible to compute the equilibrium concentrations of dislocations and grain
boundaries just as we calculated the concentration of vacancies. However, the formation
energies of these defects is so high that their equilibrium concentrations are negligible at
all normal temperatures. The energy of formation of a dislocation is of the order of 1 eV
for each plane through which the dislocation threads. The energy of formation of a grain
boundary is a fraction of an electron volt for each atom it contains (as one can see by recognizing that a low-angle, relatively low-energy grain boundary is often an array of dislocations). These defects are non-equilibrium defects in normal solids at normal temperatures.
Dislocations form and multiply not only during plastic deformation, but also during crystal growth, processing, structural phase transformations, and heating or cooling,
particularly when the material contains more than one phase. The principle source of dislocations in the latter cases are the mechanical stresses that are introduced when different
grains or phases do not quite fit together in the solid, or contract at different rates when
the solid is cooled. Since the dislocations are non-equilibrium defects there is a thermodynamic driving force to eliminate them. However, a dislocation can only disappear at a
position in the crystal where the crystal discontinuity (the extra half-plane in the case of
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an edge dislocation) can be eliminated, such as a boundary or matching dislocation of opposite sense. Dislocations are eliminated at a finite rate at moderate temperature. The
process is called recovery. However, since recovery requires solid state diffusion its rate
is relatively slow at all temperatures and is nearly zero at low temperature.
Grain boundaries are formed during the original solidification of the solid or during recrystallization or structural transformations that reconstitute the grain structure.
The grain boundaries are always non-equilibrium, high-energy defects. There is, hence, a
thermodynamic driving force to eliminate them. The smaller the grain the higher its surface-to-volume ratio; hence larger grains grow at the expense of smaller ones to decrease
the grain boundary area, causing gradual grain growth. In order for a grain to grow
atoms must move across its boundary into its interior. This diffusional process is slow at
ordinary temperatures, so grain growth only occurs at an appreciable rate at high temperature. Moreover, the decrease in boundary area per incremental increase in volume
becomes smaller as the grain grows. As a consequence the rate of grain growth decreases
as the grain size increases. In many cases the rate of grain growth is such that the grain
size increases with the square root of the aging time.
The equilibrium state of a macroscopic solid is a single crystal, and in some cases
it is possible to make single crystals by growing grains until the individual crystallites
become large enough to separate and use individually. However, in most cases it is not
practical to make single crystals by simply growing grains since the rate of growth is
slow, and the driving force for growth becomes vanishingly small as the grain size
becomes large.
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Chapter 9: Phases and Phase Equilibrium

Phases and stages
Circles and cycles
Scenes that we've all seen before...
- Willie Nelson, "Phases and Stages"
9.1 INTRODUCTION
All pure (one-component) materials take on several different structures, or phases,
as the temperature is varied at atmospheric pressure. At high temperature the material is
a vapor, at lower temperature it condenses into a liquid phase, and at still lower
temperature it freezes into a solid. Moreover, many common solids can be found in
several different crystal structures. In many cases, the multiple crystal structures of the
solid are different equilibrium phases, as in iron, which transforms from FCC to BCC as
the temperature is lowered, and in quartz, which takes on several different crystal
structures as the temperature is lowered. In other cases the multiple structures are due to
metastable equilibria. Common examples include diamond, which forms at high
temperature and pressure but can be retained indefinitely under atmospheric conditions
because of the difficulty of its structural transformation into graphite, which is the more
stable form, and silica glasses, which form from the liquid and can be retained
indefinitely because of the difficulty of the structural transformation to crystalline quartz.
When a system contains more than one component, it is often a multiphase
mixture in which volumes that have two or more distinct structures or compositions are
intermingled on a very fine scale. For example, if water that contains a small amount of
salt is held at a temperature slightly below O C it becomes a mixture of solid ice that
contains only a small concentration of salt and liquid water that is relatively salty. This
two-phase mixture persists with time, and hence must represent an equilibrium state. If
iron that contains a bit of carbon in solution is cooled from a high temperature at which
the FCC structure is preferred to a lower temperature, the iron not only transforms in
structure from FCC to BCC, but also segregates into a two-phase mixture in which small
precipitates of carbide, Fe3C, appear in a parent matrix of BCC iron that has a very small
carbon content in solid solution.
These and many other phenomena are examples of phase equilibria and
equilibrium phase transformations in solids. They can be understood and predicted from
the thermodynamic behavior of materials, and can be represented graphically in
equilibrium phase diagrams, which show the equilibrium phases that appear at given
values of the thermodynamic variables. We treat phase equilibria and phase diagrams in
this chapter.
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The principles of phase equilibria help to understand why materials have the
microstructures they do, and why these microstructures are often complex mixtures of
two or more distinct phases. However, the equilibrium behavior gives only part of the
story. To understand microstructure we must also appreciate why the equilibrium
distribution of phases is often not observed, and why the phases that do appear have the
shapes and distributions that they do. These phenomena reflect the kinetics of
transformations in materials. Even though they are influenced by kinetics, many of the
important features of real microstructures can be inferred from the equilibrium phase
diagrams, and will be discussed in this chapter. Other important features can only be
understood after a more detailed study of the kinetics of changes in solids, which will be
presented in the following chapter.
The second law of thermodynamics provides a general criterion that governs the
equilibrium of all systems: the equilibrium state of an isolated system maximizes the entropy of the system for given values of its energy, volume, and chemical content. The
material systems in which we are interested usually are not isolated, but interact with the
environment. As we discussed in Chapter 7, it is possible to rephrase the condition of
equilibrium so that it applies to a system under the experimental conditions that pertain to
it. Often the temperature and pressure are controlled by the environment, and the
chemical content is fixed. In this situation the condition of equilibrium is that the Gibbs
free energy of the material has a minimum value with respect to all changes that may
occur at the given T, P and {N}. Mathematically, if
(G)T,P,{N} 0
9.1
for all possible changes in the way the atoms are configured in the material at the given
T, P, and {N}, the system is at equilibrium. Since this is the most common experimental
situation, we ordinarily describe the equilibrium states of materials in terms of their
Gibbs free energy.
We saw in the previous chapter that the Helmholtz free energy (F) of a material is
somewhat easier to compute theoretically than the Gibbs free energy. In fact, when the
material is solid it does not matter very much whether we choose the Gibbs or the
Helmholtz free energy to describe its equilibrium states. The two differ by the factor PV:
G = E - TS + PV = F + PV
9.2
At atmospheric pressure the PV product is very small, and the Gibbs and Helmholtz free
energies are numerically almost equal. While we shall use the Gibbs free energy in the
following, we can often speak of equilibrium in the solid state as representing the
minimum free energy without being specific about which free energy is meant.
9.2 PHASE EQUILIBRIA IN A ONE-COMPONENT SYSTEM
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The phases of one-component systems (including molecular solids and

compounds with fixed composition) are distinguished by their structures. In the vapor
and liquid phases the atoms or molecules are randomly distributed, but differ in the fact
that the liquid is condensed while the vapor is not. Crystalline solid phases differ in
crystal structure. Amorphous solids (glasses) are essentially continuations of the liquid
state that differ only in properties. Phase relations like that between a liquid and a glass
are examples of what we shall call mutations, in which one phase simply becomes
another at a particular value of T and P.
The phase behavior of one-component systems can be understood by comparing
the Gibbs free energies of the various phases. In particular, we can understand why the
equilibrium phase changes, usually discontinuously, as the temperature is lowered at
constant pressure.
E + PV
-S
Fig. 9.1: The Gibbs free energy of a phase as a function of T.

Fig. 9.1 shows a plot of the Gibbs free energy of a phase as a function of temperature at constant pressure. The slope of the curve at any temperature is given by equation
7.48, and is equal to - S. Since S is positive the curve slopes down. However, as T 0
the entropy of an ordered phase vanishes according to the Third Law; even when the
phase is a non-equilibrium one that retains some entropy, the entropy becomes small.
Hence the Gibbs free energy approaches the constant value, E + PV, as the temperature
approaches zero (in the usual case PV is negligible compared to E).
9.2.1 Phase equilibria and equilibrium phase transformations
A one-component material has at least three possible phases, solid (S), liquid (L)
and vapor (V). The internal energy of these phases increases in the order S L V,
since the energy is determined by the bonding. The entropy increases in the same
sequence since the system is increasingly disordered as it changes from solid to liquid to
gas. As a consequence the Gibbs free energy curves for the three phases appear roughly
as shown in Fig. 9.2. At low temperature the solid has the least free energy and is the stable phase. Because of the higher entropy of the liquid, however, the free energy of the
liquid drops below that of the solid at the melting temperature, Tm, and the liquid is the
stable phase at higher temperature. The vapor has still higher entropy, so its free energy
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eventually falls below that of the liquid, at Tv, and the vapor phase is preferred at all
higher temperatures.
The free energy relations that lead to multiple solid structures are essentially
identical to those shown in Fig. 9.2. Suppose that a particular one-component solid has
three possible crystal structures, as shown in Fig. 9.3 and labeled , and . If the
structure has the lowest energy then it will be the equilibrium phase at sufficiently low
temperature. If another structure () has greater entropy then its free energy may drop
below that of the phase as the temperature rises. The -phase is then the equilibrium
structure. The range of preference of and phases in a hypothetical material is shown
in Fig. 9.3. The figure also includes the free energy curve for a third phase, , which does
not appear at equilibrium because its free energy is always above that of the preferred
phase.
V
L
S
G
solid
vapor
liquid
Tm
T
Tv
Fig. 9.2: Free energies and equilibrium temperatures for solid, liquid, and
vapor phases of a hypothetical material.
T
T
Fig. 9.3: Free energy relations in a material that has three phases. Note
that while phase does not appear at equilibrium, it can still
form as a metastable phase.
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9.2.2 Metastability
In addition to revealing the equilibrium state of a material, the free energy curves
also suggest how metastable phases can be formed. Suppose, for example, that the material of Fig. 9.3 is made in the phase and then cooled. The equilibrium diagram suggests
that it should transform to the phase at the temperature T. However, if the
transformation is kinetically difficult, as structural transformations generally are, then
phase may be retained at temperatures below T. When this happens the free energy
varies along the continuation of the free energy curve as the temperature drops. As the
system is cooled further the thermodynamic driving force for the transformation,
the free energy difference between the two phases, increases monotonically. If the
driving force becomes sufficient to force the transformation then will transform to at
a lower temperature. If it does not, then will be retained as a metastable structure.
The possible retention of phase in a metastable state may also make it possible
to form phase , which does not appear in the equilibrium sequence at all. When phase
is cooled below the temperature T then there is a net thermodynamic driving force for
the transformation , and this transformation will occur if it is kinetically possible.
The phase may then transform to the equilibrium phase, , but if the
transformation is kinetically difficult phase may be retained indefinitely as a metastable
phase. It is possible to form from at any temperature in the hatched region of the
figure.
Metastable behavior of the type exhibited by the , and phases in Fig. 9.3 is
common, and greatly increases the variety of structures that can be realized in
engineering solids. A classic example of the use of this behavior is the formation of an
amorphous film from a vapor phase. In this case the phase is the vapor, is the crystalline solid, and is the amorphous solid. By condensing the vapor onto a cold substrate
it is brought to below the temperature T at which it can transform to the amorphous
phase. Since the amorphous phase is kinetically easier the film takes on an amorphous
structure and is trapped in it.
Metastability also increases the variety of transformation paths that can be used in
the processing of a material. By using the metastability of the phase one can often control the temperature at which it transforms to , and can also sometimes force it to take an
indirect path in which it first forms an intermediate structure like . Since the defect type
and concentration in the microstructure of the final product is sensitive to the path of the
transformation, metastable states are often utilized in materials processing to control the
ultimate microstructure.
9.2.3 First-order phase transitions: latent heat
The phase changes that we considered above are all first-order phase transitions.
One phase transforms into another because the free energy of the product phase is lower
than that of the parent phase. The phases are distinct at the transition temperature, and
will continue to exist as metastable phases at temperatures beyond the transition
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temperature unless there is an easy kinetic path that facilitates the transformation between
them.
Transitions of this type are called first-order phase transitions because they
involve discontinuous changes in the first derivatives of the free energy function: the
entropy and the volume. The substantial majority of the phase transitions that are
important in engineering are of this type, including normal vapor-liquid and liquid-solid
transitions, and transitions between solid phases that differ in crystal structure.
Since the entropy changes discontinuously in a first-order phase transition the
transition always involves a latent heat. Heat is released or absorbed when the
transformation happens. To find the latent heat, note that the equilibrium transformation
occurs when the Gibbs free energies of the two phases are the same. When this is true,
G = 0 = E + PV - TS
= H - TS
9.3
where H is the enthalpy, H = E + PV. Hence the entropy change is

H
E
S = T ~ T
Q
=-T
9.4
Where
Q = - H ~ - E
9.5
is the latent heat of the transition, the heat released to the environment when the transformation happens.
It follows from eq. 9.5 that the latent heat is positive when the transformation is
from a relatively high-energy phase to a relatively low-energy one. Heat is released, for
example, when a vapor condenses, a liquid solidifies, or a high-temperature solid phase
transforms to a phase that is preferred at low temperature. This has the consequence, for
example, that the temperature remains almost constant while a system is undergoing a
phase transformation that happens on cooling, such as solidification. If the system is
cooled, the rate of transformation increases, and the heat released causes the temperature
to rise to the transformation temperature. The temperature cannot increase further since
the transformation would then reverse itself.
Conversely, the latent heat is negative in a transition from a low-energy phase to a
phase of higher energy, as, for example, when a liquid vaporizes or a solid melts or
vaporizes. This phenomenon is used in a number of practical ways. An intelligent but
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overheated undergraduate pours water on his head. The evaporation of water absorbs
heat and cools him. In an identical, but more high-tech example, the exposed surfaces of
missiles and spacecraft are often coated with ablative materials that vaporize at high
temperature with very high latent heat. These materials are used to cool the exposed
surfaces of a spacecraft during its re-entry into the atmosphere, since atmospheric friction
would otherwise raise the surface temperature to values that might destroy it.
9.2.4 Transformation from a metastable state
The latent heat of a transformation is only slightly changed by heating or cooling
beyond the transformation point, which reflects the fact that S and H are
approximately constant. Hence the thermodynamic driving force for transformation from
a metastable phase at a temperature T that is not too far from the equilibrium
transformation temperature, T0, is
T
G(T) = H - TS = QT - 1
0
Q
= T [T - T0]
0
9.6
Equation 9.6 is reasonably accurate even when at temperatures well below or well above
the transformation point.
9.3 MUTATIONS
9.3.1 The Nature of a Mutation
The phase changes we have considered thus far are first-order transitions that connect states that are physically different from one another. Since both of the phases in a
first-order transition are stable at the equilibrium transformation point, metastability is
always possible for at least a small range of conditions around the transformation point.
There is, however, a second type of phase transformation, in which two phases
that are otherwise distinct become identical at the transformation point. Rather than
transforming discontinuously, the two phases simply mutate into one another at the
transformation point, although they have quite different properties when they are in states
some distance away. We therefore call them mutations.
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C
'
'
Tc
T
Tc
...
Fig. 9.4: (a) The free energy curve of a system that passes through a
mutation at Tc. (b) Possible behavior of the specific heat near
the mutation.
Fig. 9.4 shows the free energy curve of a system that mutates at the temperature
Tc. The free energy curve is uninteresting and uninformative unless it is examined in
minute detail. The free energy and its first derivatives, the entropy and volume, have
well-defined values at the mutation, so the curve is continuous there to first order. A
mutation affects the second and higher derivatives of the free energy. The specific heat is
ordinarily singular at Tc, and usually has a behavior near Tc like that shown in Fig. 9.4b.
The singularities in the thermodynamic properties at Tc have the consequence that both
phases are unstable there. Metastability is impossible; the two phases become one
another at Tc.
The kind of transition we have called a mutation here is called by several other
names in the literature. The most common is second-order transition, since the transition
affects the second or higher derivatives of the free energy. Mutations whose free energy
functions resemble Fig. 9.4b near the transition point (most do) are sometimes called transitions because of the shape of the curve.
9.3.2 Common Transitions that are mutations
The simplest mutation is the glass transition we discussed in Chapter 5. At the
glass transition point, Tg, the liquid simply becomes solid. The free volume available to
the molecules in the liquid is no longer sufficient for them to move around one another,
so they are frozen into position. In contrast to the case of solidification into a crystalline
solid, there is no discontinuity in the volume at a glass transition. The discontinuities at
the glass transition occur in physical properties, for example, the coefficient of thermal
expansion changes discontinuously there.
...
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Fig. 9.5: Examples of mutations: (a) ferromagnetic crystal; (b) ordered

crystal structure of '-CuZn; (c) ferroelectric displacement in
BaTiO3.
There are also important examples of mutations in crystalline solids. However,
the requirement that two otherwise distinct phases become identical at a mutation restricts
severely restricts the kinds of phases that can be connected by a mutation. Their
crystallographic or physical symmetries must satisfy a relation called the Landau
symmetry rule. Four classes of crystalline phase transitions that are important in
materials science satisfy this rule and are always or often mutations. They are magnetic
transitions from paramagnetic to ferromagnetic or antiferromagnetic order, some
chemical ordering reactions, ferroelectric transitions, and superconducting transitions. In
each case the mutation introduces a type of order that is not present above the mutation
temperature. The first three classes of mutation are illustrated in Fig. 9.5.
Ferromagnetism and antiferromagnetism

The mutation that is probably most familiar is the ferromagnetic transition that occurs in many metals, alloys and ceramics. We shall discuss this transition in some detail
when we come to consider magnetic properties. For the moment it is sufficient to recognize that magnetic materials contain transition metals, such as Fe and Ni, or rare earth
elements that have partly filled d- or f-shells in the electron configurations of the atoms.
The electrons in the partly filled shells have aligned spins so that the ion core of the atom
has a net magnetic moment. At high temperature the magnetic moments of adjacent
atoms are uncorrelated (to maximize the entropy) so the crystal has no net magnetic
moment. In this state it is said to be paramagnetic. At a critical temperature, called the
Curie temperature, Tc, the magnetic moments spontaneously align as shown in Fig. 9.5a.
At the Curie point itself the degree of alignment is zero. However, at a temperature very
slightly below Tc there is a measurable degree of magnetic order. The degree of
alignment in the magnetic moments can be measured by the value of a long-range order
parameter, , that is zero when the spin directions are random, but takes a finite value
when the spins are aligned and approaches 1 in the limit of complete alignment. The
long-range order parameter is zero at and above Tc, but finite at any lower temperature,
as illustrated in Fig. 9.6a. At Tc the ferromagnetic and paramagnetic states become
identical; the transition is a mutation at Tc.
'
Tc
...
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Tc
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Fig. 9.6: The behavior of the long-range order parameter () near (a) a
mutation; (b) a first-order transition.
All transition metals and rare earth elements with unpaired inner shell electrons
have magnetic moments. It is a consequence of the Third Law of thermodynamics that
these moments must align at sufficiently low temperature. However, alignment does not
always lead to ferromagnetism. Adjacent magnetic moments can also align anti-parallel,
in which case they cancel one another and the crystal has no net magnetic moment. This
type of order is called antiferromagnetism, and appears through a mutation at a critical
temperature called the Neel point. There are even materials that are ferromagnetic and
antiferromagnetic at the same time. These are materials like the ferrites that have
antiferromagnetic order, but are chemically ordered so that species with different
magnetic moments appear on adjacent sites, and the net magnetic moment is non-zero.
The Curie and Neel points of these materials are the same.
Chemical order
A second class of mutations includes chemical ordering reactions like that which
leads to the '-CuZn structure (CsCl) that was discussed in Chapter 3 and is drawn in Fig.
9.5b. Above the transition point the crystal is disordered; all sites have the same
probability of being filled by either chemical specie. At the transition the lattice sites
divide into two sets, each of which is preferentially occupied by one specie. In the
example given, '-CuZn, the corner sites of the basic BCC cell are preferentially filled by
one specie while the center sites are filled by the other. Let x be the composition of the
solute in CuZn, chosen so that x .5, and let the solute fill the body-centered sites. Then
the long-range order parameter () is defined by the equation
x1 = x(1 + )
9.7
where x1 is the fraction of body-center sites filled by solute atoms. The atom fraction on
the corner sites is x2 = 1 - x1. As T0, 1 and all the solute atoms are in center sites.
As T Tc there are two possibilities. If 0 as in Fig. 9.6a the ordering reaction at Tc
is a mutation; if is discontinuous at Tc, as in Fig. 9.6b, the ordering reaction is a firstorder transition.
Only certain ordering reactions can be mutations since only these have symmetries that satisfy the Landau rule. An ordering reaction that can be a mutation may be
a first-order transition for some systems or under some conditions. Theory tells us which
reactions can be mutations; we must rely on more precise analysis or experiment to know
which of these are mutations, and under what conditions. For example, the order that creates '-CuZn from the disordered BCC solution in the Cu-Zn system is a mutation, the
order reaction that creates the Ni3Al structure from disordered FCC is always first-order,
and the order reaction that creates FeAl3 in the Fe-Al system is a mutation for one range
of composition and temperature and a first-order transition for another.
Ferroelectric transitions
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The third class of mutations that is illustrated in Fig. 9.5 is the ferroelectric transition. The classic examples of materials with ferroelectric behavior are perovskite crystals
like barium titanate (BaTiO3), which is drawn in Fig. 9.5c. The cations in BaTiO3 have a
'-CuZn configuration, which is drawn with Ti+4 in the center of the cell and Ba+2 at the
corners. At high temperature the Ti ion has a average position precisely in the center of
the cube. However, at low temperature the Ti ion is slightly displaced from the cube
center so that the cell has a permanent dipole moment. The displacement is shown,
though it is greatly exaggerated, by the arrow in Fig. 9.5c. The displacements in
neighboring cells are correlated so that the crystal has a net dipole moment and a very
high dielectric constant. This is the phenomenon of ferroelectricity, which has
technological applications in many electronic devices.
The ferroelectric transition is a mutation. Letting the order parameter, , measure
the average displacement of the central ion as a fraction of its displacement in the limit T
0, the order parameter behaves as shown in Fig. 9.6a. It vanishes at Tc, the Curie
point for the transition.
Superconducting transitions
The final class of mutations that is of great interest in materials science is the
superconducting transition, which is discussed in some detail in Chapter 19. While the
mechanism of superconductivity is not fully understood in all cases (the mechanism in
the high-Tc oxides is still under dispute) the normal source of superconductivity is the
formation of coupled pairs of electrons (Cooper pairs) that also couple to lattice
vibrations (phonons) so that they can move through the crystal without being scattered.
The ordering reaction is the formation of Cooper pairs, and it occurs through a mutation
at a specific temperature, the superconducting critical temperature, Tc.
9.4 PHASE EQUILIBRIA IN TWO-COMPONENT SYSTEMS

When a system contains more than one component it is not always meaningful to
speak of the phase that minimizes its free energy. The equilibrium state can also be a
mixture of two or more phases with different compositions. While the conditions of
equilibrium require that the temperature and chemical potentials be the same everywhere
in the system, it is possible to have the same values of the chemical potentials in two or
more phases that have very different compositions. These phases can then coexist at
equilibrium.
We shall confine this discussion to binary (two-component) systems since binary
systems are relatively easy to understand and since they exhibit most of the new phenomena that appear in multicomponent systems, such as the coexistence of phases of different
composition. Moreover, systems of engineering interest can often be treated as binary
systems, either because they are essentially binary or because the phenomena of interest
involve changing the content of one component while the remainder of the system is
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fixed in its chemistry. Phase equilibria in two-component systems are often presented in
binary phase diagrams, which are simply maps that show which phases appear at given
values of the temperature and composition. To understand the equilibrium relations that
give phase diagrams their characteristic forms it is necessary to understand the concept of
free energy curves and the common tangent rule.
9.4.1 The free energy function
Consider a two-component system for which the temperature, pressure and composition are controlled. Let the two components be labeled A and B. Let component A
be taken as the solvent, or reference component. If the mole fraction of the solute, B, is
given by the variable, x, the mole fraction of A is (1-x).
The equilibrium of the system is governed by the Gibbs free energy. The Gibbs
free energy per mole is given by the function
g = g(T,P,x)
9.8
To find the partial derivatives of the molar free energy, begin from equation 7.45 of the
previous chapter:
dG = - SdT + VdP + A dNA + BdNB
9.9
if we fix the value of N and divide through by it, the result is

dg = - sdT + vdP + Ad(1-x) + Bdx
= - sdT + vdP + (B - A)dx
9.10
Defining the relative chemical potential,

= B - A
9.11
the partial derivatives of the function g are

g
=-s
T
9.12
g
=v
P
9.13
g
= = B - A
x
9.14
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We have already studied the behavior of the free energy function as T and P are
varied. We now study the behavior of the function g(x) when the temperature and
pressure are fixed.
Three useful general statements can be made about the free energy function, g(x),
that governs a particular phase at given T and P. First, the free energy curve of a given
phase of the system must be concave, as drawn in Fig. 9.7. The slope of the curve at a
given point (say, x1) is the relative chemical potential, , defined by equation 9.14. The
condition of concavity is that
2g

=
x PT > 0
2
x
9.15
which is the condition of local stability. If 9.15 is not satisfied for a state of the system
then, as we shall demonstrate below, that state is unstable with respect to decomposition
into regions of slightly different composition and can only exist as a transient state in an
on-going transformation.
( x1)
x1
Fig. 9.7: The free energy curve of a phase of a binary system.

There is some subtlety in the definition of a phase since the free energy function
of a continuous set of states of a system, for example, a random solution of two atoms on
the sites of a FCC lattice, may include unstable states whose free energies can be
computed or even measured by achieving them in a transient sense. One example is the
simple binary solution whose free energy was computed in the previous chapter. When
the temperature is low and the relative bonding potential is positive, V > 0, its free energy
curve is like that shown in Fig. 9.8, with two minima and an intervening maximum as x is
varied from zero to one. All states in the region shown shaded in the figure, where /x
< 0, are unstable and cannot persist. Hence these states cannot meaningfully be ascribed
to any phase. The stable states, where /x > 0, are divided into two sets that fall in
different ranges of composition. The corresponding portions of the free energy curve are
marked 1 and 2 in the figure. Not only are these states stable, we shall see below that
states of 1 can coexist in equilibrium with states of 2 to form two-phase mixtures.
Hence a free energy curve like that shown in Fig. 9.8 contains two distinct phases; each
separate concave segment of the free energy curve represents a different phase.
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1
A
unstable
Fig. 9.8: Free energy curve of a system that has two distinct phases separated by a continuous set of unstable states.
An important theorem follows from this definition of a phase of a binary system:
two distinct examples of the same phase can never be in equilibrium with
one another.
This important result is a consequence of the conditions of equilibrium. If two states of
the same phase were in equilibrium then they would have to have the same values of T
and . But since /x > 0 for a given phase the chemical potential increases
monotonically with composition. Two states of the same phase cannot have the same
chemical potential, , and hence cannot be in equilibrium with one another. When a
system contains more than one distinguishable state at equilibrium, these states must be
different phases.
The second universal property of the free energy curve is its behavior in the limit
of zero concentration (x 0). It can be shown that as x 0 the relative chemical
potential takes the form
x
= 0(T,P) + RTln1-x
9.16
where 0(T,P) is a function of the temperature and pressure only. We shall not prove this
relation, which is due to Gibbs, but note that it is obeyed by the model solid solution
studied in Chapter 8. Eq. 9.16 has the consequence that the free energy curve asymptotes
to become parallel to the g-axis as x0, as drawn in Figs. 9.7 and 9.8. Since eq. 9.16
holds whatever the chemical nature of the solvent and solute, it has the consequence that
everything is at least slightly soluble in everything else.
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T2 < T1
T2 < T1
g
T1
T1
A
x0
Fig. 9.9: The behavior of the free energy curve as T decreases toward
zero: (a) solution; (b) compound stoichiometric at x0.
The third universal property of the free energy curve concerns its behavior in the
limit of zero temperature. The Third Law of thermodynamics requires that the entropy of
an equilibrium phase vanishes (or reaches a small constant value in the case of a
metastable equilibrium) in the limit of zero temperature. This has the consequence that
the free energy curve develops a sharper and sharper trough as T 0, as illustrated in
Fig. 9.9. When the phase is a random solution the free energy curve gradually folds onto
the axis, as shown in Fig. 9.9a. When the phase is a compound with a stoichiometric
composition, x0, the free energy curve becomes more and more sharply centered about
the equilibrium composition, as shown in Fig. 9.9b. This behavior has the consequence
that solubility disappears as T approaches zero; the only possible phases are pure components or stoichiometric compounds.
9.4.2 The common tangent rule
In a binary system two-phase, three-phase and four-phase equilibria are possible.
However, when the pressure is fixed it is extremely unlikely that more than two phases
will appear at equilibrium. Four-phase equilibrium requires that the pressure,
temperature and relative chemical potential have specific values. It is extremely unlikely
that the pressure of interest for a particular system would be the four-phase equilibrium
pressure. At any other pressure the maximum number of possible phases is three. But
when the pressure is fixed, three-phase equilibria occur at specific values of T and .
Since = (T,x) at given P, three-phase equilibrium requires that the temperature and
composition have mathematically precise values. But it is impossible to control these
variables to mathematically precise values in a real system. Hence only two-phase
equilibria are ordinarily observed.
Two-phase equilibria occur when the Gibbs free energy of a two-phase mixture is
lower than that of either phase alone. We can find a general mathematical condition that
must be satisfied for two-phase equilibrium directly from the conditions of equilibrium
and stability. However, there is an alternative, geometric method that is less formal and
somewhat easier to visualize.
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x - x
x - x
x
x
Fig. 9.10: Free energy curves for a binary system. The overall composition is x. A possible two-phase state would include at composition x and at x. The free energy of this state is marked
by the dot in the figure.
Consider a binary system that has two possible phase, and , at given T, P.
Possible free energy curves for the two phase are drawn in Fig. 9.10. Let the overall
composition of the system be x, as indicated by the vertical dashed line in the figure.
Since x is beyond the limit of the free energy curve, the system cannot be in a singlephase state of phase . However, it can be either in a single-phase state, phase of
composition, x, or in a two-phase state that is a mixture of and phase with different
composition. The equilibrium state is that which minimizes the Gibbs free energy.
To determine whether a two-phase state minimizes the free energy we compute
the free energy of an arbitrary two-phase mixture with net composition x. Since states of
phase cannot be in equilibrium with one another we need only consider equilibria between states of phase and states of phase . The states must be on opposite sides of the
composition, x, so that the average composition can be x.
The free energy of a two-phase mixture that has a mole fraction f of phase in
composition x and a fraction f of at composition x is
g = fg(x) + fg(x)
= g(x) + f[g(x) - g(x)]
9.17
where we have used the condition f + f = 1. The mole fraction of the phase can be
found from the condition that the overall composition is x:
x = fx + xf = x + f(x - x)
9.18
from which it follows that

x - x
f =
x -x
9.19
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Equation 9.19 is called the lever rule, since the fraction of a phase, say f, is equal to the
length on the concentration axis, x - x, on the far side of the fulcrum at x divided by the
total length, x - x.
It follows from equation 9.17 and the lever rule that
the free energy of a two-phase mixture of with composition x and

with composition x is given by the intersection of a straight line
connecting the free energies of the two states on a g-x plot with a vertical
line at the average composition, x.
This relation is illustrated in Fig. 9.10.
The equilibrium state of a binary system of overall composition, x, is given by the
phase or two-phase mixture that intersects a vertical line at x at the lowest value of g.
There are two cases. First, let the composition be such that a tangent line to the free
energy curve of the phase with least free energy never intersects the free energy curve of
the other. This situation is diagrammed in Fig. 9.12 for a case in which phase has the
least free energy. As can be seen by inspecting the figure, in this case there is no twophase combination of and that leads to a free energy below that of the phase alone.
This result is an alternative proof of the general theorem that was established in
the previous section. When the tangent to the free energy curve of the phase at x never
touches the free energy curve of the phase, phase is stable with respect to the
formation of and the equilibrium state is single-phase.
x x
x
x
...
Fig. 9.12: Free energy relations for a binary system at a composition
where the phase is stable.
Second, let the composition be such that a tangent line to the phase with the lower
free energy at x cuts the free energy curve of the other phase, as illustrated in Fig. 9.13.
In this case it is simple to find two-phase states that lead to free energies lower than that
of the homogeneous phase. It can be seen by inspection that the two-phase mixture
that provides the least free energy at composition x is a mixture of phases and with
the compositions x and x indicated in the figure. These are the states of and that
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are connected by a common tangent, a straight line that just touches the free energy
curves of both phases.
...
Fig. 9.13: Free energy relations in a binary system at a composition
where a two-phase equilibrium is stable.
Note that the same result holds for every composition between x and x, that is,
every composition of the system that is internal to the common tangent. Throughout this
range of composition the least free energy is obtained when the system is a two-phase
mixture of phase with composition x and phase with composition x. The states of
the phases in the two-phase mixture are the same for all x; however, their proportions
change according to the lever law, eq. 9.19. The rule that governs this behavior is called
the common tangent rule:
if the composition of a binary system is internal to a common tangent between the free energy curves of two phases, and if the common tangent
line lies below the free energy curve of any other possible phase, then the
equilibrium state of the system is a two-phase mixture in which the states
of the two phases are the states at the terminal points of the common
tangent and the fractions of the two phases are given by the lever rule.
9.4.3 The phases present at given T, P
We are now in a position to construct the minimum free energy curve for a system
and find the equilibrium phases as a function of composition. To do this we construct the
common tangents between the free energy curves of the possible phases. The states of
least free energy lie on a curve that can be drawn by connecting segments of the free
energy curves of the individual phases with their common tangents.
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+
x
...
Fig. 9.14: The minimum free energy curve and equilibrium phases for a
binary system at given temperature and pressure.
The minimum free energy curve for an example binary system that contains two
stable phases is drawn in Fig. 9.14. When the composition of this system is x < x, the
equilibrium state at the given values of T and P is homogeneous phase . When the composition is x > x the equilibrium state is homogeneous phase . When the composition
is in the range x < x < x the equilibrium state is a two-phase mixture of and in
which phase has composition x and phase has composition x. The relative
fractions of the two phases are given by the lever rule.
It is common to find three or more phases in a binary system as the composition is
varied at given temperature and pressure. Such a case is diagrammed in Fig. 9.15. Its
analysis is straightforward. To find the minimum free energy curve we construct the
common tangents between the free energy curves of each of the phases. The common
tangent lines join segments of the free energy curves of the individual phases. If a
segment of a single-phase curve has the lowest free energy for given composition, x, then
the equilibrium state at that composition is a homogeneous state of the preferred phase.
If a common tangent has the lowest free energy at x then the equilibrium state is a twophase mixture. The compositions of the two phases are the compositions of the states
that are connected by the common tangent. The mole fractions of the two phases are
determined by the lever rule.
x1
x2 x3
x
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Fig. 9.15: Minimum free energy surface and phase relations in a binary
system in which three phases appear at T, P.
In the case illustrated the equilibrium state of the system is a homogeneous
solution when 0 x < x1, a two phase mixture of (composition x1) and (composition
x2) when x1 < x < x2, a homogeneous phase when x2 < x < x3, a two phase mixture of
(composition x3) and (composition x4) when x3 < x < x4, and a homogeneous
solution when x4 < x 1.
More complex situations are treated in the same way. Note, however, that it is
possible for three phases, say , and in Fig. 9.15, to touch the same common tangent
line. For given pressure, this happens at a unique value of the temperature; since the
phases have different entropies their free energy curves shift by different amounts as the
temperature changes. Since it is impossible to control an exact temperature, three-phase
equilibrium is rarely important in the engineering sense. If three phases touch the
common tangent all three can coexist at equilibrium. The compositions of the three
phases are given by the compositions at which their free energy curves touch the tangent,
just as in the case of two-phase equilibrium. However, the lever rule does not apply and
their relative fractions cannot be determined from the information contained in a plot like
Fig. 9.15.
9.4.4 Equilibrium at a congruent point
In a one-component system two phases are in equilibrium when their free energies
are equal. Their equilibrium is said to be congruent because they have the same composition and can transform into one another without changing composition. A similar
situation often occurs in two-component systems; the free energy curves of two different
phases touch at particular values of T and x so that the two phases are in equilibrium
there.
An example of the situation that leads to a congruent point is drawn in Fig. 9.16b.
In order that the two-phase equilibrium at the congruent point be an equilibrium state the
free energy curves of the two phases must touch without crossing; hence they have the
same common tangent there ( = ). However, since the phases are distinct, /x
/x, so they touch only at the congruent point. It follows that if and have a
congruent point at a given temperature, one of the phases (say, ) is present in the
equilibrium state only at the congruent composition; is the equilibrium phase at all
surrounding compositions.
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x0
A
x
x0
A
x
x0
...
Fig. 9.16: Possible relation between the free energy curves of phases
and that have a congruent point at (T0,x0). (a) T > T0; phase
is stable. (b) T = T0; phase is stable, two-phase equilibrium at x0. (c) T < T0; , and + phase fields appear.
The usual reason for the appearance of a congruent point is that the system has
two phases of different entropy whose free energy curves pass through one another as the
temperature is varied, and first touch at some non-zero value of x. The situation is
illustrated in Fig. 9.16 for the case in which is a high-temperature phase whose free
energy curve is penetrated by that of the low-temperature phase as the temperature
decreases. Above the congruent point, that is, when T > T0, phase is stable at all
compositions near x0 (Fig. 9.16a). Just below the congruent point the phase appears on
both sides of the phase, with two-phase regions separating them (Fig. 9.16c). At the
congruent point the two free energy curves just touch.
9.4.5 Equilibrium at the critical point of a miscibility gap
Sometimes a phase that is stable develops an instability at an interior point of its
composition range as the temperature changes so that it decomposes into two phases.
This behavior is exhibited by many systems that are solutions at high temperature, but
decompose on cooling. An example is the model solution discussed in Chapter 8. There
are also unusual systems (long-chain polymers or complex organic systems) that
decompose on heating. The temperature and composition at which the instability that
leads to decomposition first appears is called the critical point of a miscibility gap, since a
single-phase solution divides into two phases of distinct composition (i.e., the
components become immiscible) as the state of the system passes through the critical
point.
An example of the behavior of the free energy function near the critical point of a
miscibility gap is shown in Fig. 9.17. In this case a high-temperature solution
decomposes on cooling. When the temperature is above the critical point, T > Tc, a
homogeneous solution is stable everywhere near the critical composition, xc; that is,
/x > 0 in this composition range. As the critical point is approached, /x
decreases near xc, and vanishes at xc when the critical temperature, Tc, is reached. At Tc
the phase is stable everywhere with the possible exception of the isolated point at xc.
When the temperature is below Tc there is a range of compositions about xc for which
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/x < 0, so the homogeneous state is unstable. The single, -phase has decomposed
into two distinct phases, ' and ", which produce a two-phase equilibrium at
compositions near xc. Above Tc the equilibrium state is a single-phase solution; the two
components are miscible. Below Tc the equilibrium state near xc is a two-phase mixture;
the components are immiscible in this composition range. The temperature, Tc, and
composition, xc, define the critical state at the miscibility gap.
'
"
'
xc
A
x
xc
A
x
"
'+"
xc
...
Fig. 9.17: Behavior of the free energy curve of a phase that decomposes
at a miscibility critical point. (a) T > Tc. (b) T = Tc; is stable except at the point xc. (c) T < Tc; two distinct phases, '
and " have a two-phase equilibrium at xc.
9.5 BINARY PHASE DIAGRAMS

Equilibrium phase relations are represented by phase diagrams, which are maps
that present the equilibrium phases as a function of the thermodynamic variables. The
simplest phase diagrams are binary phase diagrams that show the equilibrium phases of a
two-component system as a function of the temperature, T, and composition, x. While
the Gibbs free energy of a two-component system also depends on the pressure, the
pressure is ordinarily fixed by the atmosphere. Binary phase diagrams have the
advantage that they can be drawn in two dimensions.
While most engineering materials are multicomponent systems, binary phase diagrams are often useful for analyzing their equilibria. Many important materials have only
two dominant components, and can hence be treated as binary systems that are perturbed
by the addition of other components as minor solutes or impurities. Examples include
most alloy steels, which are solutions of Fe with C, Ni, Mn or Cr, with third, fourth, and
often fifth, sixth and seventh species included as minor alloying additions. Other
important engineering materials can be approximated as two-component systems in
which the components are compounds. Examples include many of the oxide ceramics,
which are approximately binary systems of oxide compounds. Still other engineering
materials can be approximated as two-component systems in which one element is added
against a fixed background provided by the other elements. An example that is of great
current interest is the high-temperature superconductor, YBa2Cu3O6+, whose variable
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oxygen content is expressed by the inclusion of the variable, , in the chemical formula,
where varies between 0 and 1.
The solid phases that appear when two elements are joined are of two types. The
first type is a primary solution, in which the basic structure of the phase is the structure of
the pure component, for example, phase of component A, and the second element, B, is
added to form a substitutional or interstitial solution. Since every element has at least a
small solubility in every possible phase, a primary solid solution is always formed when a
sufficiently small quantity of B is added to a phase of the pure component, A, or when
a sufficiently small quantity of A is added to phase of the pure component, B. The
second type of solid phase is an ordered compound, which is an ordered arrangement of
A and B over the sites of a crystal lattice in stoichiometric proportions that are expressed
by the chemical formula AxBy. Ordered compounds also give rise to solid solutions. It is
always possible to add some excess of A or B to the compound AxBy to create a nonstoichiometric compound which is essentially a solid solution of A or B in AxBy.
In the previous section we discussed how the equilibrium phase fields at any
given temperature and pressure are determined by the free energy curves. The phase
diagram in the T-x plane is a plot of the equilibrium phase fields as the temperature is
varied at fixed pressure. The phase fields, or regions of T and x over which the primary
solid solutions or compounds exist at equilibrium, are separated by two-phase fields in
which two phases coexist. As discussed in the previous section, the two-phase fields are
a consequence of the common tangent rule. It is also possible for three phases to be in
equilibrium at a particular value of the temperature, although three-phase equilibrium is
almost never observed in practice since the temperature cannot be precisely controlled.
Because of the possibility of forming ordered compounds at intermediate
compositions, the phase diagrams of most binary systems include a number of distinct
phases separated by two-phase regions and are very complicated in their appearance.
Whatever its complexity, however, a binary phase diagram is always just a map of the
equilibrium phases of the system A+B that contains three pieces of information: (1) the
phase or phases present at equilibrium at given temperature and composition (T,x); (2)
the compositions of the phases if the point (T,x) lies in a two-phase region; (3) the
fractions of the phases at a point in a two-phase region.
To establish this and illustrate how phase diagrams are generated from the free
energy curves we shall discuss two classic types of binary phase diagram in some detail:
the solid solution, or phase diagram of a system that forms solutions at all compositions,
and the simple eutectic, or phase diagram of a system that has two distinct phases in the
solid state. This discussion is followed by a systematic enumeration of the possible
shapes of the phase diagrams of simple systems.
9.6 THE SOLID SOLUTION DIAGRAM
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Let a binary system of elements A and B have two phases: a liquid solution (L)
that is preferred at high temperature and a solid solution (), preferred at low
temperature, in which the atoms are distributed over the sites of a particular crystal
lattice. A possible phase diagram for the system is shown in Fig. 9.18. It contains a
liquid phase at high T, a solid solution phase, , at all compositions at lower temperature,
and a two-phase +L region that separates the two. (Here, as in the following, we shall
ignore the vapor phase that appears at still higher temperature.)
L
TB
L+
T
TA
B
x
...
Fig. 9.18: Phase diagram of a binary system that forms solutions at all
compositions.
The most interesting feature of the diagram is the two-phase + L region. At the
limits of the phase diagram, x = 0 and x = 1, the binary system contains only one component. The L transition in a one-component system occurs at a particular
temperature, the melting point of the pure component in phase . Hence the two-phase
region terminates at the melting points of the two pure components, TA and TB,
respectively. Between these limits it opens out into a region in which solid and liquid
phases coexist.
9.6.1 The thermodynamics of the solid solution diagram
The two-phase region is a consequence of the difference between the shapes of
the free energy curves of the liquid and solid phases. The relevant thermodynamics are
illustrated in Fig. 9.19, which shows hypothetical forms of the free energy curves at three
temperatures. When T > TB, the higher of the two melting points, then the free energy
curve of the liquid lies below that of the phase at all compositions, and the liquid is
preferred at all compositions. When T < TA, the lower of the two melting points, the free
energy curve of the phase lies below that of the liquid at all compositions, and is
preferred. When TA < T < TB, however, the two curves intersect, as shown in Fig. 9.19b.
The common tangent rule has the consequence that when the composition lies in the
range xL < x < x both and L are present at equilibrium. The liquid has composition
xL, the solid has composition x, and the fractions of the two phases are given by the
lever rule.
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+
L
L
A
xL
B A
B A
(a)
...
Fig. 9.19: Possible free energy curves of the liquid and solid phases at
three temperatures: (a) T > TB, (b) TA < T < TB, (c) T < TA.
L
L+
xL
x
x
...
Fig. 9.20: A section of the phase diagram including an isotherm (tie-line)
that connects the equilibrium concentration xL and x.
The free energy relations drawn in Fig. 9.19 occur sequentially as the temperature
drops because the entropy of the liquid phase is higher than that of the solid. Since, for
any composition,
g
=-s
T
9.20
where s is the molar entropy, the free energy curve of the relatively low-entropy solid
phase is displaced downward with respect to that of the liquid as the temperature is lowered. In the example drawn, it first touches the liquid free energy curve at TB, and moves
through it as the temperature is lowered to TA, producing a continuous sequence of relations like that drawn in Fig. 9.19b that generate the two-phase region of the phase
diagram. At any given temperature between TA and TB the free energy curves overlap,
and the extent of the two-phase region is governed by their common tangent. Hence the
boundaries of the L+ region in the phase diagram at a temperature T such that TA < T <
TB are just the compositions xL and x that are in equilibrium by the common tangent
rule, as shown in Fig. 9.20.
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9.6.2 Equilibrium information contained in the phase diagram

Once the relation between the binary phase diagram (Fig. 9.20) and the free
energy curves (Fig. 9.15) is understood, it becomes clear that three types of information
can be found from the binary phase diagram.
First, given a temperature and composition (T,x), the equilibrium phase or phases
that appear can be read off the phase diagram by simply identifying the phase field in
which the point (T,x) lies. If the point (T,x) is in a one-phase field the equilibrium state
is a homogeneous state of that phase ( or L in the above example). If the point (T,x)
falls in a two-phase field then the equilibrium state is a two-phase mixture of the phases
that label the field ( and L in the above example).
Second, the compositions of the phases can be determined from the phase
diagram. If only one phase is present then its composition is the overall composition, x,
of the system. If two phases are present their compositions can be found by drawing an
isothermal line through the point (T,x). The compositions of the two phases are given by
the intersections of that isothermal line with the boundaries of the two-phase region, as
illustrated in Fig. 9.20. The isothermal line connecting the boundaries of the two-phase
region is called a tie-line. Note that the compositions of the two phases that are in
equilibrium depend on the temperature only, and are the same for every composition of
the system that falls within the two-phase region at that temperature. If the overall
composition of the system is changed at given T so that it remains within the two-phase
region, the fractions of the two phases change, but their compositions remain the same.
Third, the fractions of the phases present at equilibrium can be determined from
the phase diagram. If the point (T,x) falls in a single-phase region then the system
contains that phase alone. If (T,x) lies in a two-phase region then the fractions can be
computed from the equilibrium compositions at that temperature by applying the lever
rule. In the present example, for a point within the two-phase + L region,
x - xL
f = L
x -x
9.21
x - x
fL = 1 - f = L
x -x
9.22
and

In addition to showing the phases, compositions and phase fractions that are present, the phase diagram also permits an analysis of the phase changes that occur when a
system is cooled or heated slowly enough to preserve equilibrium. The most obvious difference between a one-component system and a binary system is in its solidification
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behavior. While a one-component system freezes at a particular temperature, a twocomponent system freezes over a range of temperature through a gradual increase in the
fraction of solid as the temperature is lowered through the two-phase region.
TB
L
T
TA
...
Fig. 9.21: Phase diagram indicating cooling of sample with composition x
= 0.8.
For example, Fig. 9.21 depicts the cooling of a sample of the system diagrammed
in Fig. 9.18 at x = 0.8. Following the vertical line downward shows that the system remains liquid until the temperature drops to slightly below TB, at which point it enters the
two-phase field. According to the tie-line at the top of the two-phase field, the first solid
to form within the two-phase region is rich in B, with x 0.98. As the temperature is
lowered, more and more solid appears, while the composition of the solid adjusts along
the boundary of the two-phase field, becoming progressively less rich in B. At the
same time the composition of the residual liquid evolves along the L boundary of the
two-phase field and becomes richer in A. When the temperature reaches the bottom of
the two-phase field for x = 0.8 the solidification is completed and the system becomes
homogeneous in phase at a composition of x = 0.8.
Note that two phases that are in equilibrium in the two-phase field each have uniform composition. If the system solidifies in equilibrium then on each increment of
cooling two changes occur in the solid phase: the fraction of solid increases, and the
composition of the solid evolves to the new equilibrium value. This latter change
requires that the composition of the sold that has already formed adjust to the new
equilibrium value. The composition change requires diffusion in the solid state. As we
shall see, this is a slow process in most solids, so the system must ordinarily be cooled
very slowly to maintain equilibrium during solidification.
The microstructure that results from equilibrium solidification will ordinarily be a
polygranular phase in which the grains are equiaxed and fairly large since they remain
at temperatures near the melting point for a significant period of time.
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9.7 THE EUTECTIC PHASE DIAGRAM

The second classic type of binary phase diagram applies to a system that has two
distinct equilibrium phases in the solid state, one an A-rich terminal solution, , and the
other a B-rich solution, . There must be A- and B-rich terminal solutions with different
structures when the components A and B have different crystal structures in their pure
forms. It is also possible to have A- and B-rich terminal solutions that are distinct phases
with the same structure. This happens, for example, when the system has a miscibility
gap like that shown in Fig. 9.17. Assuming a liquid solution at all compositions at high
temperature, the phase diagram of the system appears as shown in Fig. 9.22.
L
+L
+L
Fig. 9.22: A eutectic phase diagram of a binary system.

The eutectic phase diagram derives its name from the reaction that occurs where
the liquid phase field touches the two-phase + region. If the system is cooled slowly
through this point the reaction is L + , which is called a eutectic reaction.
9.7.1 Thermodynamics of the eutectic phase diagram
The free energy relations that lead to the eutectic phase diagram are shown in Fig.
9.23. The central feature is the eutectic reaction. The thermodynamic reason for this
reaction is contained in the behavior of the free energy curves near the eutectic point.
Just above the eutectic point all three phases appear in an isothermal section through the
phase diagram. The liquid phase has common tangents with both the and phases.
However, the liquid phase also has higher entropy, so its free energy curve rises with
respect to those of the and phases when the temperature is lowered. At the eutectic
point the free energy curve for the liquid just touches the common tangent between the
and curves to establish a three-phase equilibrium. Just below the eutectic temperature
the - common tangent passes below the free energy curve for the liquid phase, which
no longer appears in the phase diagram.
For any combination of the temperature and composition (T,x), the phases present
at equilibrium, their compositions and their phase fractions can be found from the phase
diagram. The label of the phase field in which the point (T,x) falls identifies the phases
that are present. If there are two phases, their compositions can be found by drawing an
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isotherm across the two -phase region that passes through the state (T,x), the tie-line
shown in Fig. 9.24. The two compositions are given by the intersections of the tie-line
with the boundaries of the two-phase region. The fractions of the two phases are given
by the lever rule.
+L
L
x2 x 3
x
x1
+L
x4
+
x1
x2
(a)
(b)
...
Fig. 9.23: (a) Free energy curves for the , and L phases just above the
eutectic temperature. (b) Free energy curves just below the eutectic temperature.
L
+L
+L
A x
x B
...
Fig. 9.24: The compositions of the and phases in equilibrium in the
state shown by the dot.
It is also possible to have three-phase equilibrium in a system with a eutectic
phase diagram, but only when the system is held at precisely the eutectic temperature.
The compositions of the three phases in equilibrium at the eutectic temperature are given
by the points at which the isotherm at the eutectic temperature touches the , L and
single-phase fields. However, the lever rule cannot be applied to determine the quantities
of the three phases. This is not an important limitation; since it is not physically possible
to control the temperature of a system to a precise point, three-phase equilibrium is not an
important case in the practical applications of binary systems.
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Characteristic phase transformations occur in a system that has a eutectic phase
diagram when it is cooled slowly enough that equilibrium phase relations are preserved.
The behavior of the system and the resulting microstructure depend on where its overall
composition falls in the phase diagram. Three distinct cases are indicated in Fig. 9.25.
x1
x2
x3
L
+L
+L
Fig. 9.25: Compositions leading to three distinct microstructures in a eutectic system.

9.7.3 Precipitation from the phase
(a)
(b)
...
Fig. 9.26: (a) Equiaxed grain structure of the primary solid solution.
(b) Precipitates of in grain interiors and on boundaries.
First consider an alloy of composition x1, which is less than the -phase solubility
limit at the eutectic temperature. Let this alloy be cooled slowly enough to maintain
equilibrium, beginning from the temperature at the top of the dotted line shown in Fig.
9.25. The system remains liquid until it reaches the temperature at which the dotted line
drops into the two-phase, + L field. It then solidifies over a range of temperature as it
is cooled through the two-phase field to become a homogeneous solid in the phase. It
remains homogeneous until its temperature drops into the two-phase, + field. At that
point a small amount of B-rich -phase precipitates out of the . The -phase increases
in volume and B-content as the temperature is decreased further.
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The probable microstructure of the system can be inferred from the equilibrium
phase diagram. If the system solidifies slowly enough to remain close to equilibrium
then the microstructure of the primary solid solution is normally a polygranular
aggregate of equiaxed grains, as shown in Fig. 9.26a. The phase typically forms as
small precipitates either in the interiors or along the boundaries of the grains (Fig.
9.26b), depending on how rapidly the system is cooled.
9.7.4 The eutectic microstructure
When the system has composition x3, the composition of the eutectic point on the
phase diagram in Fig. 9.25, its cooling behavior is qualitatively different. On cooling, the
system remains liquid until the eutectic temperature is reached. At this temperature the
system freezes completely, just as if it had a single component, but freezes into a twophase mixture of and phases whose compositions and phase fractions are given by
the tie-line and lever rule just below the eutectic temperature. If the system is cooled
further the compositions and phase fractions adjust according to the tie-lines across the
two-phase + region.
The eutectic reaction, L +, ordinarily produces a characteristic
microstructure, called the eutectic microstructure, which is illustrated in Fig. 9.27. The
elementary constituent of eutectic microstructure is a very fine-scale mixture of the two
phases in which thin plates of one phase alternate with thin plates of the other or aligned
rods of one phase sit in a continuous matrix of the other. The plates or rods are ordinarily
single crystals, but may be polycrystalline on a fine scale. The eutectic microstructure is
made up of grain-like colonies within which the plates or rods have a common
orientation.
...
Fig. 9.27: Schematic drawing of a eutectic microstructure. The grain-like
features are eutectic colonies containing aligned plates or rods.
The eutectic microstructure forms for kinetic reasons. Consider a stacking of
parallel plates of and , and let the stack grow into the liquid phase along the long axis
of the plates, as shown in Fig. 9.28. In order for the A-rich plates of phase to grow, A
atoms must diffuse from the front of the plates. If the and plates are immediately
adjacent to one another the distance the A atoms must travel is very small, and lies
entirely in the liquid phase, where the atom mobility is high. The B atoms counterflow
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through the liquid from the front of the growing plates to the plates. Hence the
eutectic microstructure grows with relative ease.
Fig. 9.28: Illustration of a growing eutectic colony.

9.7.5 Mixed microstructures in a eutectic system
The composition x2 in Fig. 9.25 lies between the solubility limit of the phase
and the eutectic composition. If a system of this composition is cooled from a
temperature at the top of the dotted line in the figure then it begins to solidify, by forming
islands of phase, when the temperature drops into the two-phase region, and solidifies
continuously as the temperature is lowered to the eutectic temperature. However, the
system is only partly solidified when the temperature reaches the eutectic line; according
to the lever rule only about 60% of the system is solid at a temperature incrementally
above the eutectic temperature. The residual liquid has precisely the eutectic
composition and solidifies by the eutectic reaction, L + . Hence the product
ordinarily has a mixed microstructure that includes islands of "proeutectic" phase that
formed during cooling through the two-phase region. These are embedded in a eutectic
constituent that formed through solidification of the residual liquid at the eutectic
temperature, as shown in Fig. 9.29.
Proeutectic
Eutectic colony
...
Fig. 9.29: Probable microstructure of a solidified sample having the composition x2 in Fig. 9.21.
Note that phase is present both in the proeutectic that formed during cooling
through the two-phase region, and in the -phase plates within the eutectic constituent.
According to the lever rule the system is about 85% just below the eutectic
temperature. This total is the sum of 60% proeutectic phase and 25% that is
contained in a eutectic constituent that is 60% and has 40% molar fraction in the
microstructure.
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9.7.6 Phase diagrams that include a eutectoid reaction

In strict metallurgical terminology the term "eutectic reaction" is reserved for a
reaction of the type L + in which a liquid solidifies to a mixture of two solid
phases. There are also many systems whose phase diagrams include points at which a
high-temperature solid solution transforms into a mixture of two other solid solutions.
The reaction is of the type +, where , and are solid solutions with different
structures. An important example occurs in the Fe-C phase diagram that governs the
behavior of carbon steels. A section of the Fe-C diagram is shown in Fig. 9.30. The
high-temperature phase is the phase, which is the FCC phase of iron, and is an FCC
solution of carbon in iron in this case. The phase diagram has a eutectic-like shape and
undergoes a reaction of the form + carbide at the bottom of the phase field.
1000
T (C)
+ carbide
800
+
+ carbide
600
0.5
1.0
1.5
weight percent carbon
2.0
...
Fig. 9.30: A section of the Fe-C diagram that includes the eutectoid reaction + carbide(Fe3C)
For historical reasons a reaction of the type +, where all three phases are
solid, is called a eutectoid reaction. The shape of the diagram and the behavior of the
system are essentially identical to those in the eutectic diagram. The eutectoid reaction
yields a eutectic-like microstructure (Fig. 9.28) for precisely the same kinetic reasons that
govern the eutectic case. If a system that has a composition below the eutectoid
composition is cooled from the field, the microstructure contains a proeutectoid
constituent as in Fig. 9.29. There is, in fact, no reason to distinguish between the eutectic
and eutectoid reactions, and we shall rarely do so in the following.
9.8 COMMON BINARY PHASE DIAGRAMS

Many binary systems contain several solid phases, and, hence, have rather
complicated phase diagrams. However, most of these diagrams can be simplified and
understood by breaking them into parts that involve the equilibrium of only a few phases.
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In this section we consider possible binary phase diagrams for systems that contain one,
two or three solid phases, and also describe one common example of a phase diagram
with two liquid phases. Almost all binary phase diagrams can be divided into segments
whose behavior is like that of one of the diagrams listed below.
9.8.1 Solid solution diagrams
The systems that form solid solutions at all compositions (at least at intermediate
temperature) have one of three phase diagrams: the simple solution diagram discussed in
Section 9.5, or a slight modification of it that has a congruent point either at the top or the
bottom of the two-phase (+L) region. Of course, solid solutions are only possible when
the two components have the same crystal structure in the solid state.
L
T
...
Fig. 9.31: The simplest phase diagram for the solid solution.
The simplest phase diagram for the solid solution is re-drawn in Fig. 9.31. This
diagram appears when the free energy curve of the solid solution first cuts the liquid free
energy curve at the higher of the two melting points of the pure components, and cuts it
last at the lower melting point, so there is no congruent point. Many binary systems have
this simple phase diagram, including Ag-Au, Ag-Pd, Au-Pd, Bi-Sb, Nb-Ti, Nb-W, CdMg, Cr-W, Cu-Ni, Cu-Pt, Cu-Pd, Hf-Zr, Mo-Ta, Mo-Ti, Mo-V, Mo-W, Ge-Si, Pd-Rh,
Ta-Ti, Ta-V, Ta-Zr, U-Zr, and V-W.
L
TB
TA
...
Fig. 9.32: Solid solution with a high-temperature congruent point.
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However, almost as many binary solutions have congruent points in their phase
diagrams, which shows that the free energy curves of the liquid and the solid solution
touch before they cross at x = 0 or x = 1. If the first contact that happens between the liquid and solid free energy curves on cooling falls at an intermediate composition then the
system has a elevated congruent point, as in Fig. 9.32. If the last contact on cooling falls
at an intermediate composition the system has a depressed congruent point, as in Fig.
9.33.
L
T
TB
TA
B
x
...
Fig. 9.33: Solid solution with a low-temperature congruent point.
There are very few binary systems with elevated congruent points; the Pb-rich
solution in the Pb-Tl system is one of the few examples. On the other hand, depressed
congruent points are common. Au-Cu, Au-Ni, Nb-Mo, Nb-Ni, Nb-V, Co-Pd, Cs-K, FeNi, Fe-Pd, Hf-Ta, Mn-Ni, Mn-Fe, Pu-U, Ti-V and Ti-Zr, show this behavior, among others. Perhaps the strangest example is the behavior of the Ti-Zr system. The high
temperature solid structures of both components are BCC, and both transform to HCP on
cooling. The phase diagram contains two solid solutions, (BCC) at high temperature
and (HCP) at lower temperature. Both the liquid- equilibrium and the - equilibrium
are separated by two-phase regions with depressed congruent points like that shown in
Fig. 9.33.
There is a simple thermodynamic reason for the preference for a low-temperature
congruent point. The molar free energy is
g = h - Ts
9.23
where h is the molar enthalpy, e + Pv, and s is the molar entropy. The high-temperature
phase is the more disordered one, and generally has a higher entropy of mixing. As a
consequence its free energy curve tends to have a deeper trough at intermediate
composition, so that the liquid and solid free energy curves contact at intermediate
composition at a temperature below the melting points of the pure components.
9.8.2 Low-temperature behavior of a solid solution
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One of the fundamental laws of thermodynamics is the Third Law, which asserts
that the entropy of an equilibrium phase vanishes in the limit T 0. The Third Law has
the consequence that a solid solution cannot be the equilibrium state in the limit of zero
temperature. At sufficiently low temperature, the equilibrium state must be a perfectly
ordered phase or a simple mixture of perfectly ordered phases. This criterion can be
satisfied in two simple ways: the solid solution can decompose into two terminal
solutions at low temperature or the system can rearrange itself into an ordered compound
or mixture of ordered compounds. The two possibilities are illustrated by the BraggWilliams model of the solid solution that is described in Chapter 8. The Bragg-Williams
solution decomposes via a miscibility gap if its components prefer like bonds, and orders
if they prefer unlike bonds.
In many real systems this low-temperature behavior intrudes at temperatures so
low that it is never observed; such systems are solid solutions for all practical purposes.
However, in other cases complete solubility is lost at moderate temperature through the
formation of either a miscibility gap or an ordered phase. We consider the two
possibilities in turn.
Phase diagrams containing a miscibility gap

A possible binary phase diagram that contains a miscibility gap is shown in Fig.
9.34. The system freezes into a solid solution () at all compositions. However, at lower
temperature the solid solution spontaneously decomposes into two solid solutions, ' and
'', that have the same structure but different compositions. The two-phase, ' + '' region within the miscibility gap contains the same information as any other two-phase
region in a binary phase diagram. The compositions of the two phases, ' and '', are
determined as a function of temperature by the isothermal tie-lines. The phase fractions
are determined from the tie-line by the lever rule.
L
''
'
A
...
Fig. 9.34: The phase diagram of a binary system that contains a miscibility gap in a homogeneous solid solution. The two-phase regions are shown shaded; the horizontal lines are the tie-lines.
A miscibility gap is caused by an instability in the free energy curve that develops
as the temperature decreases. The sequence of free energy curves that lead to a
miscibility gap like that in Fig. 9.34 were presented in Fig. 9.17. Let Tc be the
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temperature at the top of the miscibility gap. Well above Tc the free energy curve is
concave and well behaved. As Tc it approached the free energy curve flattens, until just
below Tc it develops a small convex region, as shown in Fig. 9.17. The convex region
has the consequence that two points on the free energy curve are connected by a common
tangent. Hence the system decomposes into two solutions with different compositions,
but the same structure. As the temperature decreases further the convex region becomes
more pronounced and the miscibility gap broadens. As T 0 the compositions of the
terminal solid solutions approach x = 0 and x = 1 to satisfy the Third Law.
As suggested by the Bragg-Williams model (Chapter 8), a miscibility gap is due
to a preference for bonds between atoms of like kind, with the consequence that the
energy is lowered when the system segregates into A-rich and B-rich solutions. At
higher temperature the energetic preference for decomposition is outweighed by the
entropic preference for the solid solution.
The binary systems whose components are mutually soluble at intermediate temperature, but become immiscible at lower temperature include Au-Ni, Au-Pt, Cr-Mo, CrW, Cu-Ni, Cu-Rh, Ir-Pa, Ir-Pt and Ta-Zr. Ceramic systems such as NiO-CaO also form
solid solutions with low-temperature miscibility gaps. According to the Third Law, the
miscibility gap must extend to the pure component lines at T = 0, as drawn in Fig. 9.34.
Not all of the diagrams that appear in compilations of binary phase diagrams are drawn
this way since decomposition is kinetically slow and difficult to observe at low temperature.
Phase diagrams with low-temperature ordered phases

L
...
Fig. 9.35: Phase diagram of a binary system that has an ordered phase ()
at low temperature. The two-phase regions are shaded with
horizontal tie-lines.
The phase diagram of a binary system that forms an ordered phase at low
temperature is shown in Fig. 9.35. The single-phase region of the ordered phase is closed
at a congruent point at its top (T0) and asymptotes to a point in the limit T 0, to satisfy
the Third Law. The conditions at the two limiting temperatures have the consequence
that the ordered phase field has a shape something like that of an inverted teardrop. At
finite temperatures the ordered phase has at least a slight solubility for the species A and
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B, and is in equilibrium over a range of compositions about its stoichiometric value. The
single-phase field is bounded by two-phase (+) fields that separate it from the singlephase field on either side. If only one ordered phase is present, then the two-phase
regions that bound it must spread across the phase diagram in the limit T 0 so that the
equilibrium phases at T = 0 are the stoichiometric ordered phase and the phase at x =
0 or x = 1, in agreement with the Third Law. In many systems that order, several ordered
phases are present.
The free energy relations that give rise to a phase diagram like that in Fig. 9.35
are illustrated in Fig. 9.36. The free energy curve of the ordered compound lies above
that of the solid solution when T > T0 and passes through it to create a congruent point
at T = T0. The free energy curve of the ordered phase has a strong minimum at its
stoichiometric composition. When T < T0 the free energy curve of the phase lies below
that of the solid solution only at compositions near the stoichiometric value. Hence
there are common tangents between the and free energy curves on both sides of the
curve. The phase is the equilibrium phase at compositions near the stoichiometric
value; the phase is at equilibrium at compositions that deviate significantly from the
stoichiometric value to either side.
...
Fig. 9.36: Free energy relations leading to the appearance of an ordered
compound: (a) T > Tc; (b) T < Tc.
Many binary systems whose components have complete or extensive solid
solubility at intermediate temperature are known to order into one or more stoichiometric
compounds at lower temperature. Examples include Au-Cu, Cu-Pt, Cd-Mg, Co-Pt, CuPd, Fe-Ni, Fe-Pt, Fe-V, Mn-Ni, Ni-Pt, and Ta-V.
9.8.3 Phase diagrams with eutectic or peritectic reactions
Binary systems that have two distinct phases in the solid state often have phase
diagrams of the simple eutectic or peritectic (inverted eutectic) form.
The eutectic diagram
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The simple eutectic diagram was discussed in some detail in Section 9.5, and is
re-drawn in Fig. 9.37. It takes its name from the eutectic reaction,
L+
9.24
which occurs at the minimum point of the liquid phase field.

A system that has a eutectic phase diagram is usually one whose components have
different crystal structures in the pure form. Since components with different structures
cannot form a continuous range of solid solutions, there are always at least two phases in
the solid state and the eutectic diagram is one of the simplest the system can have.
Among the systems with simple eutectic diagrams are Ag-Bi, Al-Ge, Al-Si, Al-Sn, AuCo, Au-Si, Bi-Cu, Bi-Cd, Bi-Sn, Cd-Pb, Cu-Li, In-Zn, Pb-Sb, Pb-Sn, Si-Zn and Sn-Zn.
Ceramic systems with simple eutectic diagrams include MgO-CaO, among others. All of
these systems have components with different crystal structures, and are sufficiently
different chemically that it is plausible that they form no stable compounds.
L
T
...
Fig. 9.37:
A binary system with a simple eutectic diagram. The twophase regions are shown shaded with horizontal tie-lines.
However, there are also systems that have simple eutectic phase diagrams even
though their components have the same crystal structure. Examples include Ag-Cu, in
which both components are FCC, Cd-Zn, both components HCP, and Na-Rb, both components BCC.
L
L
B A
+L
+L
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...
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Fig. 9.38: Free energy relations leading to a eutectic diagram for a system
whose components have a miscibility gap at high temperature.
(a) Liquid phase stable; (b) three phases appear at lower T; (c)
two solid phase appear below the eutectic point.
The most plausible interpretation of the eutectic behavior in this case is that the
two terminal solutions have a miscibility gap at a temperature so high that the liquid
phase is retained to temperatures well below Tc. The relations between the free energy
curves that lead to a eutectic diagram in a system whose solid phases have a miscibility
gap is diagrammed in Fig. 9.38. Fig. 9.38a diagrams a situation in which a solid phase
has decomposed into two solutions with the same structure, and , at a temperature at
which the liquid is still stable. As the temperature decreases the solid free energy curve
drops with respect to the liquid, and leads to a eutectic diagram. Fig. 9.38b shows the
situation just above the eutectic point where all three phases appear. Fig. 9.38c shows the
situation just below the eutectic point where only and solid solutions appear at
equilibrium.
The peritectic diagram

The classic peritectic phase diagram is drawn in Fig. 9.39. It is characterized by
the appearance of a peritectic reaction of the form
+L
9.25
that appears at the top of the field.

L
...
Fig. 9.39: A simple peritectic phase diagram in a binary system.
The peritectic reaction is, essentially, an inverse eutectic. The classic eutectic
reaction occurs when the free energy curve of the liquid cuts through a common tangent
to the curves of two solid phases on heating. The peritectic occurs when the free energy
curve of a solid phase cuts through a common tangent to the curves of liquid and solid
phases on cooling. The relations between the free energy curves just above and just
below the peritectic point are illustrated in Fig. 9.40. Just above the peritectic the
common tangent to the L and phases lies below the free energy curve, as in Fig.
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9.40a. At the peritectic the free energy curve contacts that common tangent, and drops
below it as the system is cooled further to create the configuration shown in Fig. 9.40b.
Simple peritectic diagrams are much less common that simple eutectic ones. The
thermodynamic reason is apparent from Fig. 9.40. To create a peritectic point the free
energy curve of the solid must cut that of the liquid at finite x, that is, at a composition
away from the axis. For that to happen the free energy of the solid phase must decrease
more quickly than that of the liquid at small x. Since the liquid has higher entropy, this is
only likely to happen when the enthalpy of the solid phase drops rapidly with the solute
content, that is, when there is a strong preferential bonding between the two components
in the phase. But this is precisely the situation that leads to the formation of stable
compounds between the two components. A system that has a simple peritectic diagram
is, therefore, likely to be one that almost forms stable compounds.
L+
L
L+
B
x
...
Fig. 9.40: Free energy relations leading to a peritectic phase diagram. (a)
T just above the peritectic temperature; (b) T just below.
Examples of metal systems that have peritectic diagrams are Cu-Nb, Cu-Co, NiMo, Ni-Re, Ni-Ru, Os-Ir, Os-Pd, Re-Rh, W-Pd and W-Pt. Not surprisingly, some of
these systems, such as Ni-Mo, form intermetallic compounds at lower temperature.
There are also several examples of systems that have peritectic reactions in which the
high-temperature solid phase is an intermetallic compound. Examples include Al-Al3Ti,
Al-Al3Zr and Al-AlSb.
L
L
B A
+L
BA
Fig. 9.41: A peritectic reaction in a system with a high-temperature miscibility gap. (a) The liquid phase is stable at a high temperature below the miscibility gap in the solid; (b) two-phase equi-
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librium just above the peritectic; (c) two-phase equilibrium

below the peritectic temperature.
There is at least one example, Ag-Pt (FCC), in which two components with the
same crystal structure have a peritectic phase diagram. As in the case of a eutectic
diagram between elements with the same structure, this suggests that the components
have a high-temperature miscibility gap, leading to free energy relations like those shown
in Fig. 9.41. The condition is that the second solid phase that intersects the liquid curve
( in the case shown) makes its first appearance as a stable phase by cutting the tie-line
between the liquid and the solid solution.
9.8.4 Structural transformations in the solid state
When one of the components of a binary system undergoes a structural
transformation on cooling, not only is a new structure introduced into the binary phase
diagram, but new two-phase equilibria appear. Since the phases that are connected by the
structural transformation are different, they respond differently to the introduction of the
solute. The result is a two-phase equilibrium field between them. Figs. 9.42 and 9.43
show the common forms of the binary phase diagram of a system in which one
component (A) undergoes a structural transformation ( ) as the temperature is
lowered. The configurations at the solid-solid transformation are geometrically identical
to those at the eutectic or peritectic points of the liquid-solid transformation.
L
+L
T
+L
+
+
A
...
Fig. 9.42: A binary system with a eutectic reaction at the bottom of the
liquid phase field and a eutectoid reaction at the bottom of the
phase field of the high-temperature () phase. The two-phase
fields are shaded with isothermal tie-lines.
If is the low-temperature phase of a component (A) that also has a hightemperature phase, , then the free energy of falls below that of as the temperature is
lowered. On the x=0 axis (where the system has only one component) the two free
energies cross at a particular transition temperature. However, since the two phases are
distinct they respond differently to the solute, and hence have different free energy curves
at finite x. As these curves pass through one another they generate a two-phase region,
just as in the liquid-solid case. The shape of the two-phase (+) region depends on
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where the free energy curve first contacts the curve as the temperature is lowered. If
the first contact is between the and curves rather than between the curve and the -
common tangent then the behavior is just like that near a eutectic point in the liquid-solid
case; the high-temperature phase field () extends to a temperature minimum at finite x,
as shown in Fig. 9.42. The reaction at the bottom of the field is
+
9.26
This reaction is called a eutectoid reaction since it is eutectic-like, but involves only solid
phases. In the writer's opinion the separate terminology is redundant.
In a system that has a eutectoid reaction the first contact between and is
ordinarily at x = 0, in which case the phase diagram near the reaction looks like that
shown in Fig. 9.42. However, it is also possible that the first contact occurs slightly off
the x-axis at finite composition. In this case the field has a maximum at a congruent
point between and , while the field has a minimum at a eutectic point at slightly
higher composition. We shall not illustrate this case.
Eutectoid reactions are common in binary systems that include a component that
transforms in the solid state. We discussed the case of the transformation in FeFe3C in Section 9.5. Other examples include the transformation of Ti in Ti-Cr and
Ti-W, the transformation in Mn in Ni-Mn, and the transformation in Th in
Th-U and Th-Zr. Eutectoid reactions also occur in the transformations of many
intermetallic and oxide compounds.
The second possibility is that, on cooling, the free energy curve cuts the -
common tangent before it contacts the free energy curve. Then the situation near the
transition temperature is like that illustrated for the peritectic transition in the liquid-solid
case. The phase field extends to a temperature maximum at finite x, and the configuration near the transition has a shape like that drawn in Fig. 9.43. The reaction at the maximum point of the field is
+
9.27
and is called a peritectoid reaction.
L
T
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...
Fig. 9.43: A binary system with a eutectic reaction at the bottom of the
liquid phase field and a peritectoid reaction at the top of the
phase field of the low-temperature () phase. The two-phase
fields are shaded with isothermal tie-lines.
Peritectoid reactions are reasonably common. Examples include the
transition of Fe in Fe-Nb and Fe-Ta, the transition of Co in Co-Cr and Co-W, and
the transition of Mn in Mn-Cr. Peritectic reactions are also found in a number of
intermetallic and oxide compounds.
9.8.5 Systems that form compounds
A substantial fraction of all binary systems form ordered compounds in the solid
state. In fact, it is common for several compounds to appear in the phase diagram. To
explore the influence of ordered compounds on the shape of the phase diagram we consider systems that contain a single one. Fig. 9.35 illustrates the phase field of a
compound that emerges directly from a solid solution. We now consider compounds in
systems that contain two terminal solid solutions. Four cases are reasonably common: (1)
a compound first appears at a congruent point in the liquid; (2) a compound first appears
at a peritectic point in a two-phase region (+L); (3) a high-temperature compound
disappears at a eutectoid; (4) a low-temperature first appears at a peritectoid. Finally, we
consider the equilibrium phase fields near a structural transformation of an ordered
compound.
Compounds that form directly from the liquid

Many binary systems have stable compounds that can be formed directly from the
liquid at a congruent point. The simplest phase diagram for a system of this type is
shown in Fig. 9.44. The compound essentially divides the phase diagram into two
eutectic diagrams between the compound and the terminal solid solutions.
L
...
Fig. 9.44: The phase diagram of a system that forms a stable compound at
an intermediate composition.
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Phase diagrams like that shown in Fig. 9.44 govern a large number of binary systems, including Al-Sb, Al-Ca, Al-Au, As-In, As-Pb, Ca-Mg, Nb-Cr, Cd-Sb, Cd-Te, CrTa, Cr-Zr, Ga-Sb, Hf-V, In-Sb, Mg-Pb, Mg-Si, Mg-Sn, Mo-Pt, Pb-Te, Sn-Te, and Zn-Te,
among others. Phase diagrams of this type are particularly common in the III-V and IIVI systems. In these cases the stable compounds are the semiconducting III-V and II-VI
compounds.
The reaction at the congruent point in Fig. 9.44 is L , where is the compound. Compounds that form congruently are particularly easy to make since they can be
gotten by direct solidification (casting or crystal growth) from a liquid of appropriate
composition. Phase diagrams of this type are basic to a number of technologically
important processes. Perhaps the most important is the growth of large crystals of III-V
and II-VI semiconducting compounds from the melt, which is only possible when the
compound has a congruent point with the liquid.
Compounds that form through a peritectic reaction

If a binary system contains a single compound () whose free energy curve is such
that its first appearance breaks a solid-liquid (+L) tie-line then the compound is derived
from a peritectic reaction ( + L ) and the simplest phase diagram is like that shown
in Fig. 9.45.
...
Fig. 9.45: The phase diagram of a binary system with an intermediate
compound that forms by a peritectic reaction.
Several binary systems that have phase diagrams that closely resemble Fig. 9.45,
including Bi-Pb, Cd-Sn, Hg-Pb, In-Pb, Hf-W, Mo-Zr, Ru-W and Sn-Tl. The phase diagrams of Mo-Hf and Sb-Sn differ from Fig. 9.45 only in that the phase at the far end of
the phase diagram has a peritectic rather than a eutectic relation to . The phase diagrams
of many binary systems that form multiple compounds are such that some of these compounds form through peritectic reactions and have local phase relationships like those in
the left-hand side of Fig. 9.45.
Because the compound in Fig. 9.45 is the product of a peritectic reaction it
cannot be cast or grown directly from the melt. Moreover, many of the more useful
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compounds of this type include elements that diffuse slowly in the solid state so that it is
difficult to make the compound by holding the system at a point within equilibrium phase
field. Technologically important compounds that have this behavior include the A15
superconducting compounds such as Nb3Sn and Nb3Al, high-temperature intermetallic
structural materials like Ni3Al, and low-density intermetallics with potential hightemperature structural applications such as the Al-Ti intermetallics. Complex processing
techniques such as reaction from a ternary solution, vapor deposition, or powder
processing are required to synthesize these compounds.
Finally, note that a phase diagram like that shown in Fig. 9.45 has a eutectic reaction, but the phases that border the eutectic include intermediate compounds ( in the figure). Nonetheless, a system that has the eutectic composition will solidify into a eutectic
microstructure like that illustrated in Fig. 9.27. One or both of the interleaved phases are
intermetallics rather than terminal solid solutions.
Compounds that disappear at a eutectoid

Many binary phase diagrams contain ordered compounds that only appear at
intermediate temperature. They are stable at high temperature, but eventually disappear
if the system is cooled. For this to happen in a simple system that contains only one
ordered compound the common tangent to the free energy curves of the terminal solid
solutions must fall beneath the free energy curve of the compound at sufficiently low
temperature. This is more likely to happen if the terminal solution is more stable than the
compound, and is hence most often observed in systems whose compounds result from a
peritectic reaction like that shown in Fig. 9.45.
Fig. 9.46 contains a sketch of a simple phase diagram containing a single ordered
compound that is confined to intermediate temperature. The top of the phase field of the
compound is a peritectic point, +L . The phase field terminates in a eutectoid reaction, +.
...
Fig. 9.46: Phase diagram of a simple binary system that forms a compound at intermediate temperature.
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Several binary systems have phase diagrams that resemble Fig. 9.46 very closely,
including Bi-Pb, Cd-Sn and Ru-W. Many other systems contain compounds whose thermal stability is limited by the intrusion of other ordered compounds.
Compounds that form at a peritectoid

If an intermetallic compound first appears in the solid state then it intrudes either
into a single-phase region or a two-phase region. In the former case the maximum temperature of the equilibrium field of the compound is a congruent point, as in Fig. 9.35,
where the compound forms by a reaction of the type . In the latter case the
maximum temperature is the temperature at which the free energy curve of the compound
cuts a two-phase tangent line. The top of the field is a peritectoid point, and the
compound forms by a reaction of the type + .
A simple phase diagram for a binary system with a compound that forms by a
peritectoid reaction is shown in Fig. 9.47. Several binary systems have phase diagrams
that resemble this one, including Ru-Mo, Ru-Nb and Pd-V. In binary systems that
contain several compounds it is common that one or more appear at low temperature
through peritectic reactions.
L
...
Fig. 9.47: Phase diagram of a simple system in which a compound appears through a low-temperature peritectoid reaction.
Structural transformation of a compound

Compounds may undergo structural transformations just as pure phases do. In
fact, there is a richer set of possibilities for transformations in compounds, since compounds can change in chemical order as well as in basic lattice structure.
A compounds transforms when there are two separate phases of essentially the
same compound (nearly the same stoichiometric composition) whose free energies
become equal at some temperature and composition. If the high-temperature phase of the
compound were cooled to that temperature and composition it would transform homogeneously to the low-temperature phase. If the two phases are related by a first-order
transformation, that is, if they are distinct phases at the transformation point, then they
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are represented by different free energy curves and their first contact on lowering the
temperature is at an isolated point.
A compound differs from a pure component in that its composition can deviate
from stoichiometry in either the positive or the negative sense. At finite temperature the
free energy curve of a compound is continuous through its stoichiometric composition (as
illustrated, for example, in Fig. 9.25) and its chemical potential is not singular there. This
has the consequence that the free energy curves of two phases of essentially the same
compound (that is, compounds that have the same stoichiometric composition in the limit
T 0) may first touch one another on cooling at a composition that is off-stoichiometric
and possibly outside the equilibrium phase field of the high-temperature phase.
The two possibilities are illustrated in Fig. 9.48, which shows free energy curves
at a temperature just above that at which a compound, , transforms to a second
compound, , in a system whose phase diagram is like that in Fig. 9.44 at temperatures
above that shown. In the left-hand figure the free energy curve of the phase contacts
that of the phase within its region of stability. In the right-hand figure the free energy
curve contacts the common tangent between the phase and the primary solution.
B A
A
x
...
Fig. 9.48: Possible shapes of the free energy curves near the transformation . (a) The free energy curve contacts within the
stability range. (b) The free energy curve contacts the -
common tangent.
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L
...
Fig. 9.49: Phase diagram of a binary system in which a high-temperature
compound, , transforms to a low-temperature compound, , at
a congruent point, as in Fig. 9.48a.
The situation shown in Fig. 9.48a leads to a phase diagram like that shown in Fig.
9.49. The contact of the and free energy curves gives rise to a congruent point in the
phase field at which without change of composition. The congruent point is enclosed by two-phase (+) fields that terminate at eutectic points for the reactions
+ and +.
Structural transformations of compounds that lead to a phase relationship like that
drawn in Fig. 9.49 occur in a number of binary systems, including W-C, Ag-Ga, Ag-Li,
Au-Zn, Cu-In, Cu-Sn, Mo-C, Mn-Zn, Ni-S, Ni-Sn and Ni-Sb.
When the configuration of the free energy curves near the structural
transformation resembles that in Fig. 9.48b, the low-temperature phase, , first appears as
the product of a peritectic reaction, + . The given fact that becomes stable means
that the curve is displaced downward relative to the free energy curve as the
temperature decreases. The form of the phase diagram near the peritectic can be
approximated by translating the free energy curve in 9.48b downwards as T decreases
and constructing the successive common tangents. The resulting phase diagram is drawn
in Fig. 9.50. The and stability fields never touch; they are separated by a narrow twophase region that terminates at a eutectic point where the reaction is + .
L
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Fig. 9.50: Phase diagram for a system in which a compound transforms

through a peritectic reaction, as in Fig. 9.48b.
Compound structural transformations of the type that appears in Fig. 9.50 are
found in many binary phase diagrams. Among the systems that have reactions of this
type are Ag-Cd, Ag-In, Bi-Mg, Co-Cr, Ge-Cu, Cu-Sn, Hf-Ir, Mn-Ni, Mn-Pt, Mn-Zn, MoPt, Ni-V, and Zn-Sb. As this extensive list suggests, the geometry of the transformation
in Fig. 9.50 is, in fact, more common than that the congruent geometry shown in Fig.
9.49. Its prevalence reflects the narrow width of the equilibrium phase fields of most
solid compounds; a small difference in the relative composition dependence of the free
energies of the two phases can then shift the first intersection of the two curves out of the
stability field of the high-temperature phase.
9.8.6 Mutation lines in binary phase diagrams
The kind of phase transition known as a mutation, or second-order phase
transition, was discussed in Section 9.3. In a mutation, one phase simply becomes
another. There is no two-phase equilibrium and, hence, there are no two-phase regions
associated with mutations.
However, in a binary system the critical temperature for a mutation can be a function of composition, and almost always is. Hence the mutation appears as a simple curve
in a pseudo-single phase region that contains both of the phases that are related by the
mutation. There is also no discontinuity in the boundary of the pseudo-single phase region where the mutation line contacts it. The composition of the phase in equilibrium in
a two-phase region is fixed by temperature. Hence a mutation line is a horizontal
isotherm through a two-phase region that gives the temperature at which one phase
mutates.
L
T
'
A
...
Fig. 9.51: A eutectic system with a mutation in the terminal solid solution, indicated by the dashed line.
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L
'
...
Fig. 9.52: A binary system with an intermediate compound that undergoes a mutation, indicated by the dashed line.
Fig. 9.51 illustrates the appearance of a eutectic phase diagram with a mutation in
the -rich solid solution. The ferromagnetic transition in Fe and Ni and the rare earths
leads to phase relationships like those shown in Fig. 9.51. Fig. 9.52 illustrates the phase
relationships in a simple system with an intermediate ordered phase that mutates. Many
intermediate compounds undergo ordering reactions that are mutations. The classic
example is the ' transition in Cu-Zn.
9.8.7 Miscibility gap in the liquid
As a final example we consider a binary system in which a miscibility gap
intrudes in the liquid, as it does in many real systems. The simplest system of this type
has only the two terminal solid solutions in the solid state. The phase diagram is drawn
in Fig. 9.53.
L1
L2
...
Fig. 9.53: A possible phase diagram for a binary system with a miscibility
gap in the liquid. The shaded region is an equilibrium between
two liquid phases.
A sequence of free energy relations that lead to a phase diagram like that shown
in Fig. 9.53 is drawn in Fig. 9.54. Fig. 9.54a pertains to a temperature just below the
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melting point of the phase. The miscibility gap in the liquid is due to the inflection in
its free energy curve, which divides it into two stable phases with a common tangent.
The three phases , L1 and L2 appear in the section. Fig. 9.54b is drawn at a lower
temperature at which the liquid phase L1 no longer appears. As shown in the diagram the
free energy curve of the phase has dropped with respect to that of the liquid, with the
consequence that the lowest common tangent connects the and L2 free energy curves
directly. The free energy curve is everywhere above that of L2. As a consequence
there are two phases in the section, and L2. Fig. 9.54c illustrates behavior at a still
lower temperature where both the and free energy curves are well below that of the
liquid. The lowest common tangent in this case connects and directly; only these
phases appear in an isothermal section through the phase diagram.
L'
+ L'
L'
L'+L"
L'
L"
L"
B A
L"
+L"
L"
B A
L'
L"
...
Fig. 9.54: Free energy relations at three temperatures in a system with the
phase diagram shown in Fig. 9.53: (a) just below the melting
point of ; (b) at a T where only and L2 appear; (c) at a T
where only and appear.
The binary systems that have phase diagrams that resemble Fig. 9.53 include AlBi, Al-In, Bi-Zn, Cu-Cr, Cu-Pb, Cu-Tl, Ni-Pb, Pb-Zn and Th-U. These systems contain
species that are very different in their chemical behavior, which leads to the miscibility
gap in the liquid. A like behavior is seen on the silica-rich side of the SiO2-MgO
diagram.
Similar phase relations are found at low temperature in the solid state in a number
of systems that form extensive solid solutions, including Al-Zn, Nb-Zr and Hf-Ta. Phase
fields like those in Fig. 9.53 result from a miscibility gap in the solid solution. In the case
of Al-Zn the miscibility gap has a bottom because of its interaction with the terminal Zn
solid solution. In Nb-Zr and Hf-Ta the bottom of the miscibility gap is due to
interference by the low-temperature phase of one of the components; both Hf and Zr have
structural transformations at low temperature.
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Chapter 10: Kinetics

Many years ago, on a visit to Korea
I was introduced to a famous palmist.
After examining my palm, he noted that I have an
exceptionally long "life line"
"Great", I said, "does that mean I can expect a
long, long life?"
"Perhaps." he replied, "It is not just the length of the line,
but how fast you are moving along it."
10.1 INTRODUCTION
The science of kinetics is concerned with the rate of change. Thermodynamics
sets the driving forces that impel changes of state; kinetics determines how quickly those
changes happen. When the process can happen in more than one way, the relative
kinetics also determine the path taken in a change of state; the system evolves along the
path that permits the most rapid rate of change. The path that is preferred kinetically
does not necessarily lead to the preferred equilibrium state. It may, instead, terminate in
a metastable state where the system is trapped and cannot evolve further. This fact is
central to materials processing, which is the art of manipulating the microstructure to
control engineering properties. To achieve a desired microstructure one brings the
system into a non-equilibrium state that is chosen so that the desired microstructure is
both thermodynamically possible and kinetically achievable. Once the desired microstructure is established, one changes the forces or constraints on the system to "freeze"
the microstructure so that it is retained for at least the intended service life of the
material.
It is useful to divide changes of state into two types that are based, respectively,
on internal and global equilibrium. Internal equilibrium requires that the temperature (T),
the pressure (P) and the chemical potentials {} have uniform values. If any of these
conditions is violated, the material evolves to re-establish it. A local gradient in the
temperature causes a flow of heat, a local gradient in the pressure causes a mechanical
relaxation that redistributes the volume, and a local gradient in the chemical potential
induces a flow of the associated chemical species. These are, ordinarily, continuous
changes of state that do not change the basic structure, or phase of the material.
The stronger condition of thermodynamic equilibrium is the global condition of
equilibrium, which asserts that the total entropy of the system and its environment should
be as large as possible or, equivalently, that the appropriate thermodynamic potential of
the system should be as small as possible. Changes of state that result from violations of
the global conditions of equilibrium are called phase transformations. They are discon-
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tinuous transitions in the sense that the microstructure is physically different after the
transformation has happened.
We shall defer the discussion of phase transformations to the following chapter,
and consider the kinetics of continuous transitions here. We shall specifically describe
the conduction of heat in solids and the diffusion of chemical species through solids.
While the microstructural mechanisms of heat and mass flow are very different, they are
governed by a differential equation, called the diffusion equation, that has the same form
for both.
Heat is transported by particles whose motion is controlled by collisions with the
lattice and with one another. Kinetic processes of this sort are called frictional processes.
A familiar example is the fall of a solid body through the air; its terminal (steady state)
velocity is determined by the balance between the force of gravity, which tends to
accelerate it, and the frictional force of the air, which is due to collisions with air
molecules that tend to slow it down.
Mass diffusion through solids ordinarily occurs by discrete atom jumps from one
equilibrium site to another. In moving from site to site the atom must pass through intermediate positions in which it has a relatively high energy. The energy required to pass
through these intermediate configurations is supplied by thermal fluctuations. Kinetic
processes of this type are called thermally activated processes. Diffusion in the solid
state is a prototypic example.
This chapter begins with a discussion of heat transfer as an example of a
continuous transition. This example is followed by a brief introduction to the general
theory of continuous transitions, called non-equilibrium thermodynamics. The chapter
concludes with the analysis of diffusion in solids.
10.2 LOCAL EQUILIBRIUM

We ordinarily describe the states of systems that are not in equilibrium by giving
the distribution of the thermodynamic forces within them, with the understanding that, if
the thermodynamic forces are not uniform, the system will evolve in a direction that
makes them so. For example, we describe a material that is heated on one side as having
a non-uniform temperature. Strictly speaking, it is incorrect to do this. Temperature is a
characteristic of thermodynamic equilibrium, and is not well defined when the conditions
of equilibrium are violated. (As an example, those of you who are studying chemical or
mechanical engineering may have already encountered the practical problem of
measuring the temperature of a flowing fluid, and learned that the temperature you
measure may depend on how the measurement is done.) However, provided that the
system is not too far from equilibrium we can construct a perfectly useful theory that uses
equilibrium properties like the local temperature and entropy and chemical potential. It is
worth taking a moment to consider how this can be done.
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To apply equilibrium thermodynamics to non-equilibrium states we use the assumption of local equilibrium. In most of the continuous transitions that are of interest in
materials science, the deviation from equilibrium is imperceptible on the atomic scale.
The variation in temperature or composition is significant on a scale of millimeters, and
possibly micrometers (microns), but even a micron corresponds to several thousand
interatomic spacings. Moreover, the rate of change of thermodynamic quantities is
usually very slow compared to the processes that establish equilibrium on the atomic
level. The electron cloud around an atom adjusts itself at a natural frequency that is
called the plasmon frequency, and is about 1015 cycles per second, and the atom as a
whole vibrates with a mean frequency on the order of 1013 cycles per second. In
contrast, sensible changes in the temperature ordinarily require at least a fraction of a
second and significant chemical redistributions require minutes or hours. In the usual
situation, an atom comes to an essentially complete equilibrium with its immediate environment long before it senses any macroscopic violation of the conditions of equilibrium. It is, therefore, usually reasonable to assume that any microscopic subvolume of a
material is locally in equilibrium at any instant of time.
x1
dV(R)
R
x2
Fig. 10.1: Macroscopic system divided into differential subvolumes.

We can construct a non-equilibrium thermodynamics of continuous processes in
the following formal way. Let the system have total volume, V, and let it be divided into
subvolumes, dV, that are microscopic, but still large on the atomic scale (Fig. 10.1).
Each differential volume is instantaneously in equilibrium so that it has well-defined
values of the thermodynamic variables. The position of a particular volume element, dV,
can be designated by its vector position, R, in a coordinate system fixed in space. It has
the instantaneous temperature T(R), pressure P(R), and chemical potentials {(R)}.
When the thermodynamic state is non-uniform these are continuous functions of the
position variable, R.
When two adjacent differential volumes are not in equilibrium with one another
their interaction changes the state of the system. They exchange heat and mass across
their fixed boundaries. The process by which this happens can be modeled by replacing
the system by an idealized one that remains in equilibrium at all times. Let the
differential volume elements be separated by partitions that isolate them from one
another, but periodically become transparent so that heat or mass can move across them.
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While the partitions are impermeable each differential volume element comes to
equilibrium. When the partitions are transparent each element exchanges incremental
quantities of heat and mass with its neighbors. The time interval between periods of
transparency is taken to be long enough to establish internal equilibrium, but short
enough that the system seems to evolve continuously on the time scale that is pertinent to
macroscopic changes. Each differential volume element of the ideal system is in a welldefined equilibrium thermodynamic state at any instant of time. However, the system as
a whole is in a non-equilibrium state that changes continuously. We use this idealized
system to model and predict the behavior of real systems in non-equilibrium situations.
The simplest case of non-equilibrium behavior is the conduction of heat through a
material whose pressure and composition are fixed. We consider this case first, and then
return to a discussion of the general equations of non-equilibrium thermodynamics.
10.3 THE CONDUCTION OF HEAT

10.3.1 Heat conduction in one dimension: Fourier's Law
Consider a solid whose atoms are immobile, so that atomic diffusion can be neglected, and assume that the temperature varies in the x-direction, T = T(x). This means
that two adjacent subvolumes have different temperatures, as shown in Fig. 10.2.
According to the Second Law, the temperature difference induces a flow of heat across
the boundary, as shown in the figure. The heat flow (Q) is in the direction of decreasing
temperature and vanishes when the temperature difference vanishes. The simplest
equation that has these properties is
Q = - C(T)
10.1
where C is a positive constant.
JQ
T2
T1
Fig. 10.2: Heat flow from one differential volume to another in response
to a temperature difference, T2 > T1.
The constant, C, in equation 10.1 cannot be a material property since both the
temperature difference, T, and the heat flow, Q, depend on the specific geometry of the
differential volume elements. When the local temperature variation is small the
temperature difference can be written
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dT
T = dx x
10.2
where x is a coordinate in the direction that connects the centers of the volume elements,
x is the distance between the centers and dT/dx is the temperature gradient in the
direction, x. The flow of heat per unit time from one volume element to the other can be
written
Q = JQ dA
10.3
where dA is the area of the interface and JQ is the heat flux perpendicular to the interface,
the heat flow across the interface per unit area per unit time. Substituting equations 10.2
and 10.3 into 10.1 yields the relation
dT
JQ = - k dx
10.4
Equation 10.4 relates the heat flux to the temperature gradient. The equation
holds independent of the geometry of the differential volume elements, and the coefficient, k, is a material property, which is called the thermal conductivity. Equation 10.4 is
the one-dimensional form of Fourier's Law of Heat Conduction. According to equation
10.4 the local deviation from thermal equilibrium produces a driving force, the
temperature gradient, dT/dx. The response to this force is a thermodynamic flux, JQ, in a
direction that would relieve the driving force. The magnitude of the flux induced by a
given force is determined by the thermal conductivity, which is a property of the material.
When heat flows in accordance with Fourier's law it may or may not change the
temperature of the volume element that receives it. For the temperature to change there
must be an accumulation of energy in the volume element, which only happens if there is
a net flux of heat across its boundary. To find the equation that governs the temperature
change consider the one-dimensional case shown in Fig. 10.3.
JQ
23
JQ
12
T3
T2
T1
Fig. 10.3: One-dimensional flow of heat.

Heat flows into the central volume element in Fig. 10.3 from the left, and flows
out across the interface to the right. The net heat added per unit time, QT, is
Q Q
QT = J23 - J12 dA
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10.5
Materials Science
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where dA is the interface area. If the volume element is small and the flux is continuous
then the flux at the 12 interface is related to that at the 23 interface by
dJQ
Q
Q
J12 = J23 + dx dx
10.6
where dx is the length of the volume element. It follows that

dJQ
d dT
QT = - dx dV = dxk dx dV
10.7
where we have used Fourier's Law (equation 10.4). When the temperature of a
differential volume element is changed by dT at constant volume (dV) and composition
the change in energy is equal to the heat added, and is proportional to the change in
temperature:
dE = dQ = CvdTdV
10.8
where Cv is the isometric specific heat. Dividing equation 10.8 by the time differential,
dt, substituting equation 10.7, and dividing through by the volume, dV, we obtain the
partial differential equation that determines the change in the temperature as a function of
position and time, that is, the partial differential equation that determines the function,
T(x,t),
T(x,t)
=
k
T(x,t)
t
Cv x x
10.9
When the thermal conductivity is constant this simplifies to

T
k 2T
=
t
Cv x2
10.10
The partial differential equation 10.10 is an example of the diffusion equation,

whose solutions are tabulated in standard texts on differential equations.
10.3.2 Heat conduction in three dimensions
In a more typical case the temperature is a function of position in threedimensional space, and is described by the function, T(R,t), where
R = x1e 1 + x2e 2 + x3e 3
10.11
is the position vector, and x1, x2, x3 are the coordinates of the point, R, in a Cartesian coordinate system with the unit vectors e 1 , e 2 , e 3 . In the three-dimensional case the local
variation in the temperature is described by the gradient,
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T
T
T
T = x e 1 + x e 2 + x e 3
1
2
3
10.12
which is a vector that has both magnitude and direction. The heat flux that is induced by
the temperature gradient is also a vector, J Q .
The equation that relates J Q to T (the three-dimensional form of Fourier's Law)
is complicated by the fact that the heat flux is not necessarily parallel to the temperature
gradient. The component of the heat flux in the direction e 1 depends on all three components of the temperature gradient:
T
T
T
Q
J1 = - k11x - k12x - k13x
1
10.13
where k11, k12 and k13 may be different material constants. The other two components
of the heat flux obey similar equations. Hence there are a total of nine thermal
conductivities of the form kij (i,j = 1,2,3). These nine coefficients obey the symmetry
relation, kij = kji (for example, k12 = k21) and, hence, only six of them are independent.
However, the most general material still has six independent thermal conductivities.
Fortunately, equation 10.13 has a much simpler form in most of the cases of interest to us. Equations like 10.13 that describe the behavior of materials are called
constitutive equations. A constitutive equation must predict a behavior that is compatible
with the symmetry of the material; if the direction of the temperature gradient is changed
to a symmetrically equivalent direction, as from one <100> direction to another in a cubic
crystal, then the direction of the induced flux must change in exactly the same way. A
material with an amorphous structure is the same in every direction, and is said to have
isotropic symmetry. A material that has a cubic crystal structure is said to have cubic
symmetry. It can be shown that the symmetry of an isotropic or cubic material has the
consequence that the off-diagonal coefficients, kij (i j), vanish, while the diagonal
components, kij (i = j), are all equal. Hence when the material is isotropic or cubic the
heat flux is parallel to the temperature gradient
J Q = - kT
10.14
where the thermal conductivity, k, has the same value in all directions. In a cubic or
isotropic material the heat flux in each of the three coordinate directions obeys an
equation of the form 10.4, for example,
T
Q
J1 = - k x
10.15
Most materials of engineering interest are isotropic or cubic to a good approximation. Amorphous solids and glasses are isotropic, materials with cubic crystal structures
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are cubic, and polygranular materials that are aggregates of many crystalline grains with
random orientations (random polycrystals) are isotropic in the macroscopic sense
whatever their crystal structures. Hence the vector form of the Fourier Law of Heat
Conduction given in equation 10.14 is usually adequate.
When the material is cubic or isotropic the three-dimensional equation that
governs the change in the temperature with time can be derived by considering the total
rate of accumulation of heat in a cubic volume element. The heat flow along each of the
three coordinate directions obeys an equation of the form 10.15, and the total heat
accumulated per unit time is obtained by summing the heat contributed by flow in the
three coordinate directions. It follows from equation 10.7 that
Q
Q
Q
J1 J2 J3
QT = - x + x + x dV
1
2
3
= - (^J Q )dV
10.16
where the symbol ^J Q is the vector notation for the quantity in brackets, and is called
the divergence of the vector J Q . Using equation 10.8 and assuming that the thermal
conductivity is constant, it follows by a derivation analogous to the one that leads to
equation 10.10 that the temperature distribution through the body, T(R,t), is governed by
the partial differential equation
T
k 2T 2T 2T
=
t
Cv x12 + x22 + x32
k
=C
2T
10.17
where symbol 2T is a vector notation for the quantity in brackets, which is called is
called the Laplacian of T.
10.3.3 Heat sources
The temperature change in a differential volume of the solid may also be affected
by the presence of heat sources, where heat is created, or heat sinks, where heat is lost. If
there are heat sources or sinks distributed through the volume that produce a net heat, q,
per unit volume per unit time then equation 10.16 must be changed to
QT = - [^J Q + q] dV
10.18
so that the evolution of the temperature is governed by the partial differential equation
T
Cv t = k2T + q
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The most common heat source is a chemical reaction or first-order phase

transition within the volume that produces a latent heat, QL, per mole of product. The
latent heat was discussed in Chapter 7. It may be positive or negative. A phase transition
to a high-temperature phase is endothermic; heat is absorbed and QL is negative. The
rate at which heat is evolved per unit volume of material, q, is the product of the latent
heat per mole and the number of moles created per unit volume per unit time, n:
q = QLn
10.20
A second source of heat added to a volume of material is the absorption or

emission of radiation. The most common type of radiation is the thermal radiation
between bodies of different temperature, which gives rise to a heat flux that is
proportional to the fourth power of the temperature. Thermal radiation provides a heat
source or sink at the external surface of an opaque body. The net flux to a surface at
temperature T from a medium of temperature T0 is
JQ = aB(T04 - T4)
10.21
where (a) is the absorption coefficient for the material and B is the Stefan-Boltzmann
constant.. The absorption coefficient is a material property that depends both on the
nature of the material and on the nature of its surface. The more reflective the surface,
the lower the value of the absorption coefficient.
There is also a net radiative heat transfer from point to point within a material
whose temperature is non-uniform. However, this internal radiative transfer is included
in the thermal conductivity. According to equation 10.21, radiant heat transfer in an
opaque body gives a contribution to the thermal conductivity that is proportional to T3.
This contribution is negligible except in semi-transparent materials at very high
temperature.
The absorption of radiation creates a heat source when the radiant photons are absorbed at discrete sites within the body. Examples include x-rays and energetic ions,
which penetrate well into a solid before being absorbed, and light photons in a
transparent body, which are often absorbed at discrete impurity atom sites (color centers)
that are distributed through the body. Radiation can also create an effective heat sink, for
example, when energy is liberated by the radioactive decay of atoms within the material.
10.4 MECHANISMS OF HEAT CONDUCTION

Heat is transported through a solid by three carriers: lattice vibrations, conduction
electrons, and optical photons. Since elementary lattice vibrations can be treated as particles, called phonons, as we discussed in Chapter 7, all three cases can be visualized as
heat conduction by energetic particles that move through the solid. In the course of their
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motion they occasionally collide with one another or with the crystal lattice itself. These
collisions produce an effective friction that opposes their motion.
The type of carrier that is mainly responsible for the transport of heat depends on
the type of material and the temperature, and is also sensitive to the microstructure.
Phonons are the predominant carriers in all materials at very low temperature. Electrons
become the predominant carriers in metals at moderate temperature. Photons are
relatively unimportant except in insulators at very high temperature.
10.4.1 Heat conduction by a gas of colliding particles
The basic equation that governs thermal conductivity can be derived by
considering thermal conduction in a dilute gas of particles that collide with one another.
The theory of this process was originally developed to treat the thermal conductivity of a
gas of atoms, but also provides a reasonable description of thermal conduction by "gases"
of electrons, phonons or photons in solids.
Assume a gas of particles that move at an average velocity, v, that is randomly
oriented in space. The particles occasionally collide with one another. Assume that they
travel an average distance, l, the mean free path, between collisions, where l = v and
is the mean time between collisions. Let the gas have a temperature, T(x), that varies in
the x-direction, and assume that the particles come to thermal equilibrium at the local
value of the temperature when they collide.
J = (1/2)nev
...
Fig. 10.4: Flux of particles in one dimension. The particles in the region
shown that travel in the positive direction cross the shaded surface in unit time.
Now let an imaginary plane be placed perpendicular to the x-axis, as shown in
Fig. 10.4. The number of particles that cross the plane in the positive direction per unit
1
time is 2 nvx, where vx is the average speed of travel in the x-direction and the factor 1/2
appears because half of the particles are moving in the positive x-direction at any given
time. If these particles carry an average energy, , then the net flux of energy across the
plane in the positive x-direction is
1
1
J+ = 2 nvx = 2 EV(T)vx
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where EV(T) (= n) is the energy of the mobile particles per unit volume, which depends
on the temperature. The typical particle that crosses the plane had its most recent
collision a distance of the order lx away, where lx is the mean free path of travel in the
x-direction between collisions. Hence
1
J+(x) = 2 EV[T(x-lx)]vx
10.23
where J+(x) is the flux in the positive direction across a plane at x, and EV[T(x-lx)] is
the energy density at the position, x - lx, where the previous collisions occurred. The
energy density depends on the position, x, through the local value of T at that position.
Since particles move in both directions along the x-axis, there is also a flux of energy across the plane in the negative x-direction, equal to
1
J-(x) = 2 EV[T(x+lx)]vx
10.24
Hence the net flux in the positive x-direction across a plane at x is

1
J(x) = 2 vx{EV[T(x-lx)] - EV[T(x+lx)]}
10.25
Let the temperature gradient be constant over the mean free path, lx, as it is, at least approximately, when lx is a microscopic distance and the temperature variation is macroscopic. Then
dEVdT
EV[T(x-lx)] = EV[T(x)] - dT dx lx
dT
= EV[T(x)] - Cvlx dx
10.26
where Cv is the isometric specific heat. If we write a similar relation for the energy
density at x + lx, and substitute the two relations into equation 10.25, the result is
dT
J(x) = - Cvvxlx dx
10.27
which has the form of Fourier's Law for heat conduction, with the thermal conductivity
k = Cvvxlx = Cvvx2
10.28
where is the mean time between collisions. Since the particles are equally likely to
move in any direction,
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1
vx2 = vy2 = vz2 = 3 v2
10.29
where v is the average particle speed, and

1
1
k = 3 Cvv2 = 3 Cvvl
10.30
where l is the mean free path.

Equation 10.30 is valid whatever the nature of the conducting particles, provided
that they travel with velocity, v, and equilibrate by collisions with the mean free path, l.
The electrons, phonons and photons that carry heat through a solid behave in this way.
10.4.2 Heat conduction by mobile electrons
Conduction electrons are the primary carriers of heat in metals at normal temperatures. This may seem surprising, since we found in Chapter 8 that the specific heat is primarily due to lattice vibrations (phonons). However, while the phonon specific heat of a
metal at room temperature is roughly an order of magnitude greater than the electron specific heat, electrons travel at speeds approaching the speed of light, 108 cm/sec, while
phonons travel at the speed of sound, 105 cm/sec. Hence the electrons make a greater
contribution to the thermal conductivity. In a pure metal at room temperature the
electron conductivity is 30 times the phonon conductivity. In a disordered alloy it is
roughly 3 times greater.
The mean free path of the electrons is determined by their collisions with the
crystal lattice. These collisions transfer energy to the lattice and cause the electron
distribution to equilibrate at the local value of the lattice temperature. The electronlattice collisions are also responsible for the electrical resistance of the metal, and we
shall discuss them further when we treat electronic properties. The collisions have two
sources: collisions with phonons and collisions with defects, primarily solute or impurity
atoms. Both types of collisions are due to the interaction of the electron with a local
disturbance of the crystal pattern of the ion cores.
If the solid were a perfectly ordered crystal in which all ion cores were sited in
their equilibrium positions, the valence electrons would not interact with the lattice at all.
The reason is that the electrons are in quantum states that are determined by the ion
configuration. The interaction with the ions is incorporated into the wave function of the
electron itself. The similar situation in the free atom is, perhaps, more familiar. The
electrons in an atom orbit around the nucleus. Their interaction with the nucleus
determines the wave functions that describe their states. They do not collide with the
nucleus in any other way as they move about in the ion core.
In a real crystal the perfect pattern of the ion cores is disturbed in two ways.
Because of thermal oscillations the ions are not instantaneously situated on their
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equilibrium sites, and in the neighborhood of defects or solutes the charge distribution is
locally disturbed by the different charge distribution of the solute and the distortion of the
positions of the lattice atoms around it. Hence a traveling electron "sees" lattice
vibrations and defects as disturbances in the perfectly periodic charge distribution its
wave function is designed to expect. Its motion is perturbed by these disturbances. We
describe the perturbation by saying that the electron periodically "collides" with them and
is "scattered" by them. The mean free path between collisions of conduction electrons
and phonons in a pure metal at room temperature is 100-600. The mean free path
between collisions with solute atoms is of the order of the mean separation of the solutes,
and is, hence, proportional to n-1/3, where n is the number of impurity atoms per unit
volume.
The collisions between the electrons and the lattice determine the electrical
conductivity as well as the thermal conductivity, so we might expect the two to be
related. The relation between them is known as the Wiedemann-Franz Law,
LT
k = LT =
10.31
where L is a constant, called the Lorenz number, is the electrical conductivity, and =
1/ is the electrical resistivity. The Wiedemann-Franz Law can be understood by
referring back to equation 10.30. The electrical resistivity, , is inversely proportional to
the mean free path, l, since the motion of an electron through the lattice is resisted by its
collisions. The electronic specific heat, CV, is proportional to the temperature, T, as we
found in Chapter 8. Hence the product, CVl, yields a relation of the form given in
equation 10.31.
The resistivity of a typical metal varies linearly with the temperature:
= 0 + bT
10.32
where 0 is the residual resistivity, due to solutes, impurities and lattice defects, and the
linear increase in with T is due to electron collisions with lattice phonons. This simple
equation leads to the following rough approximation for the thermal conductivity:
LT
k ~ + bT
0
10.33
At high temperature the thermal contribution to the resistivity dominates, and

L
k~b
10.34
so the thermal conductivity approaches a constant. At low temperature the residual resistivity, 0, dominates the denominator, and
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LT
k~
0
10.35
so thermal conduction by electrons increases approximately linearly with T. The lowtemperature limit, equation 10.35, is only reached in alloys and defective metals with
high values of 0, since, as we shall see, phonon conductivity becomes dominant at
sufficiently low temperatures.
The thermal conductivity of a metallic solid solution (alloy) is always much lower
than that of the pure metal because of its higher residual resistivity, 0. Highly alloyed
materials, such as stainless steels, have relatively low thermal conductivities. A familiar
example of the engineering application of this result is in the design of stainless steel skillets, which are sometimes plated with high-conductivity copper to distribute heat and prevent the development of hot spots in the skillet. For the same reason aluminum kitchen
foil is made of aluminum that is alloyed as little as possible.
10.4.3 Heat conduction by phonons
Lattice vibrations, or phonons, are the principle carriers of heat in all materials at
very low temperature, and dominate the thermal conductivity of insulating materials at all
but very high temperatures.
When a solid is heated, for example, on one of its surfaces, the local increase in
temperature excites lattice vibrations that propagate through the lattice. Since the
vibrations are harmonic waves, we can picture them as particles (phonons) that move
through the lattice. The phonons experience two distinct types of collisions: they collide
with one another, and they collide with defects in the lattice, such as solute atoms.
Phonon-phonon collisions
Phonon-phonon collisions occur because the interatomic forces are slightly anharmonic, as discussed in Chapter 8. Because of this anharmonicity, an atom that is initially
given a simple harmonic vibration gradually changes its frequency. We can model this
process by saying that lattice phonons excite one another by collisions.
As we discussed in Chapter 8, a one-dimensional lattice vibration is described by
a wave function of the form
u(x,t) = u0 exp[i(kx - t)]
10.36
where u(x,t) is the displacement of an atom at position, x, at time, t, k is the wave vector
of the vibrational wave, and is its frequency, which depends on k through the
dispersion relation. The wave vector, k, lies in the range - /a k /a that defines the
first Brillouin zone, where a is the atom spacing in the x-direction.
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The momentum of the lattice wave is given, in quantum mechanics, by the

relation
u
px = - ix = k
10.37
Hence conservation of momentum in phonon-phonon collisions requires that the total

wave vector be conserved. If phonons with wave vectors k1 and k2 collide to produce
phonons with wave vectors k3 and k4, we must have
k1 + k2 = k3 + k4
10.38
so the net direction of propagation of the lattice waves is not changed.

However, it is possible to have a phonon-phonon collision that is consistent with
equation 10.38 in which one of the product vectors exceeds the value, /a. We saw in
Chapter 8 that a phonon with k /a is indistinguishable from one with
2
k' = k - a
10.39
Hence when a collision produces a phonon with k /a, it is indistinguishable from one
with k' = k - 2/a; a large fraction of its momentum is apparently lost. This momentum is
not actually lost from the system. It is transferred to the crystal lattice. However, it is
lost from the phonon spectrum. Since the net phonon momentum decreases, the net
transport of energy by phonons goes down, and the phonon thermal conductivity is
diminished.
Inelastic phonon collisions of this sort are called Umklapp processes, and they are
responsible for the finite value of the phonon thermal conductivity in a solid. A more
elaborate analysis shows that an equation of the form 10.30,
1
k = 3 Cvvl
10.30
applies to the phonon conductivity, k, where Cv is the vibrational specific heat and l is
the mean free path of the phonons between inelastic collisions.
The mean free path between inelastic collisions is strongly dependent on the temperature. A simple relation can be found from the following one-dimensional argument.
Since inelastic collisions require a product phonon with k /a, and since momentum is
conserved, these collisions will involve at least one phonon with an initial wave vector, k
/2a. In the Debye model these phonons have energies, E kD/2, where D is the
Debye temperature. The mean free path between such collisions should decrease with the
density of these high-energy phonons, giving
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1
l fi n(k /2)
D
10.40
where n(kD/2) is the equilibrium density of high-energy phonons. We found in Chapter

8 that the equilibrium density of phonons with energy, , has a simple form in the highand low-temperature limits:
e- /kT
n() ~
kT
>> kT
<<kT
10.41
Using this relation in eq. 10.40, the mean free path for inelastic phonon-phonon collisions
obeys the relation
eD/2T
l fi
1/kT
T << D
T>>D
10.42
Equations 10.42 are obeyed by most pure crystalline materials. For temperatures
above D, the phonon mean free path varies inversely with temperature. Hence the thermal conductivity of an insulator decreases as T increases above D until photon
conductivity intrudes at very high temperature. As T decreases below D, on the other
hand, the mean free path between phonon-phonon collisions becomes very large. As a
consequence, all pure crystalline materials have high thermal conductivities at
temperatures well below D. The low-temperature value of the thermal conductivity is
limited by the defect density. The phonon mean free path is determined by defect
scattering rather than by phonon-phonon interactions when the temperature is sufficiently
low.
Phonon-defect collisions
The second kind of collision that limits the phonon mean free path involves collisions with lattice defects, such as solute atoms, grain boundaries, dislocations,
precipitates, or, in the case of a glass, irregular atom configurations. The mean free path
for phonon collisions with defects depends on the type of the defects as well as on their
separation. Defects that dramatically disturb the crystal lattice, such as free surfaces,
pores, precipitate particles and grain boundaries, interact strongly with phonons. When
these are the dominant scattering centers the mean free path is equal to the mean defect
spacing. The distorted atom configurations in glasses scatter phonons strongly. The
effective mean free path in a silica glass is 3-5 , which is of the order of the size of a
basic silica tetrahedron.
Solute atoms are less effective scattering centers. The phonon mean free path in a
solid solution is proportional to the mean solute separation, but is greater, since, effectively, only a fraction of the phonon-solute collisions cause phonon scattering. The
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phonon mean free path for collisions with solutes decreases as the temperature rises, and
becomes nearly constant when T D/2.
Phonon thermal conductivity

When several different phonon scattering processes are active, the total number of
collisions per unit time is the sum of the collisions due to each scattering process. Since
the frequency of collisions is inversely proportional to the mean free path, the net value
of mean free path is determined by the reciprocals of the mean free paths for each
independent mechanism:
1
1
1
l = l1 + l2 + ...
10.43
where l1, l2, refer to the different collision mechanisms. It follows that the mean free
path at a given temperature, and, hence, the phonon conductivity, is dominated by that
process whose mean free path is the smallest. The result is a phonon conductivity that
varies with temperature as drawn schematically in Fig. 10.5. Two curves are drawn in
the figure to illustrate the characteristically different behaviors of a pure, crystalline solid
and a highly defective solid such as a glass.
Crystal
Glass
T
...
Fig. 10.5: The variation of thermal conductivity with temperature for a
crystal and a glass.
In a pure crystalline solid the concentration of defects is small, so the associated
mean free path is large. At normal temperatures the mean free path is determined by
phonon-phonon collisions. It is useful to distinguish three temperature regimes.
(1) T > D. When T is above the Debye temperature, D, the specific heat is
constant and the phonon mean free path is inversely proportional to the temperature (eq.
10.42). It follows that the phonon conductivity, k, is given by a relation of the form
1
A
k = 3 Cvvl ~ T
(T D)
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where A is a constant.
(2) 0 << T < D. At lower temperatures the mean free path for phonon-phonon
collisions increases exponentially (eq. 10.42). When T is low and phonon-phonon collisions dominate thermal conductivity,
k A'eD /2T
(0<<T << D)
10.45
where A' is a pre-exponential factor.

(3) T 0. The mean free path for phonon-phonon collisions increases with decreasing T, and, eventually, exceeds the mean free path for phonon-defect collisions with
whatever defect dominates scattering in the material (usually grain boundaries). When
this happens, l becomes fixed. Since Cv varies as T3 at low temperature, the thermal
conductivity obeys a relation of the form
k = A"T3
(T 0)
10.46
Note that the thermal conductivity vanishes in the limit of zero temperature.
Equations 10.44-46 are obeyed rather well by crystalline materials that are
electrical insulators, except at very high temperatures where photon conductivity
becomes important. Pure metals also conduct heat primarily via phonons at low
temperatures. The thermal conductivities of pure metals have the characteristic shape
given in Fig. 10.5 for temperatures less than about half the Debye temperature (T <
D/2). At higher temperatures the electronic contribution dominates the thermal
conductivity. For this reason the thermal conductivities of metals are much higher than
those of insulators when they are compared at the same value of the dimensionless
temperature, T/D, for T greater than about D/2.
At temperatures near room temperature almost all the best thermal conductors are
metals, and they are the materials that are the best electrical conductors, such as Cu, Ag,
Au and Al. However, there are a few simple insulators that have very high Debye
temperatures. These materials are also excellent thermal conductors at normal
temperatures, since their phonon thermal conductivities are unusually high. Diamond,
which has a Debye temperature near 2000 K, is the best thermal conductor known at
temperatures near room temperature.
Glasses and highly defective crystalline solids are relatively poor thermal conductors at all temperatures. The phonon mean free path in such a material is necessarily
small because of the high concentration of defects. Except at high temperature, the mean
free path is nearly constant, so the temperature dependence of the thermal conductivity is
determined by the specific heat. Hence the thermal conductivity decreases with the
temperature, and obeys equation 10.43 as the temperature approaches zero. At normal
temperatures the thermal conductivity of a glass is small relative to that of the same
material in crystalline form. However, as the temperature increases the mean free path
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for phonon-phonon collisions in the crystal decreases, eventually becoming comparable

to that in the glass. The crystal and glass have similar thermal conductivities at high
temperature.
Amorphous polymers that are electrical insulators (as are almost all of them)
behave like glasses. Their thermal conductivities are small and decrease with
temperature.
10.4.4 Heat conduction by photons
A body that has the temperature, T, radiates energy in the form of photons with an
intensity that is proportional to T4. There is, hence a radiant heat transfer between bodies
of different temperature that is proportional to the difference between the fourth powers
of their temperatures (see equation 10.21):
JQ = K(T14 - T24)
10.47
where the constant, K, depends on the thermal emissivities of the bodies.

Equation 10.47 suggests that there is a radiant heat transfer between regions of
different temperature in a solid. This transfer is negligible at all temperatures unless the
solid is transparent to photons at frequencies near the peak of the thermal spectrum,
which shifts from the infrared at low temperatures into the visible spectrum at high
temperature (the spectral peak in the thermal emission of photons is responsible for the
characteristic color of the glow of a hot metal, and is used to measure the temperature by
instruments known as optical pyrometers).
In a transparent solid the radiant heat transfer contributes an additive term to the
thermal conductivity,
kr = ArlT3
10.48
where Ar is a constant and l is the mean free path for photons. Even in these materials
the radiant contribution to the thermal conductivity is negligible until the temperature is
very high. It is responsible for a gradual increase in the thermal conductivities of
transparent insulators that becomes significant at temperatures above about 1000 K.
The principle engineering interest in the radiant thermal conductivity lies in
reducing it. It is a source of increased thermal conductivity in the ceramic materials that
are used as thermal insulators at high temperature. Radiant conduction is particularly
important in transparent glasses which conduct heat poorly by other mechanisms.
To decrease the radiant contribution to the thermal conductivity one decreases the
photon mean free path by introducing microstructural defects that scatter light. The most
effective defects are grain boundaries in polycrystalline ceramics and small voids or
pores in both crystalline ceramics and glasses. Both grain boundaries and pores are efPage 292
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ficient reflectors (you can easily verify, for example, that typical opaque sand consists of
small grains of transparent material). The photon mean free path, l, is equal to the
distance between such scattering centers. Hence the radiant conductivity decreases
significantly if the grain size of a polycrystalline ceramic is refined, or if a high density of
fine pores is introduced into a ceramic or glass. For this reason thermal insulators that
are intended for use at high temperature tend to be porous compacts of polycrystalline or
glassy ceramics.
The walls of thermally insulating containers usually have a sandwich design
whose center is an open space that is evacuated (hence the term vacuum bottle). Thermal
radiation is the only mechanism available for heat conduction across an evacuated space.
To minimize it, the walls of the evacuated space are silvered to make them highly
reflective, so that the incident thermal energy is reflected rather than absorbed on the cold
side of the evacuated space.
10.5 NON-EQUILIBRIUM THERMODYNAMICS

Now that we have learned a bit about the simplest continuous transition, the conduction of heat, it is worthwhile to consider the general theory of continuous changes before turning to our second specific example, the diffusion of atoms through solids.
10.5.1 The thermodynamic forces
The conditions of local equilibrium in a simple solid require that the temperature,
pressure, and chemical potentials of all components be constant. When these conditions
are violated they give rise to thermodynamic forces whose local values are given by the
gradients, T, P, and {}, where {} is the set of all chemical potential gradients.
This list contains (n+2) thermodynamic driving forces, where n is the number of
chemical components.
However, only n+1 of the thermodynamic forces are independent. This is a
consequence of a general relation in thermodynamics that is known as the Gibbs-Duhem
equation, which states that the changes in T, P and {} are related by the differential
equation:
n
SdT - VdP +
Nkdk = 0
10.49
k=1
Equation 10.49 can be solved for one of the differentials dT, dP, or any one of the dk. It
follows that the gradients of the thermodynamic intensities are related by the equation
n
ST - VP +
Nkk = 0
k=1
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and, hence, that only n+1 of the gradients are independent.

It is usually best to choose the independent forces so that the conditions of
thermal, mechanical and chemical equilibrium are most clearly separated. To do this we
divide equation 10.50 through by the total mole number, N, to obtain
n
sT - vP +
ckk = 0
10.52
k=1
where s is the molar entropy, v is the molar volume, and ck = Nk/N is the mole fraction of
the kth component (we shall use the symbol ck rather than xk to avoid confusion with the
coordinate, x). Since the mole fractions sum to 1, the mole fraction of the nth component
(the solvent) is given by the equation
n-1
cn = 1 -
ck
10.53
k=1
When this equation is substituted into equation 10.52 the result can be cast in the form
n-1
n = - sT + vP -
ckk
10.54
k=1
where k is the relative chemical potential of the kth component,

k = k - n = c g(T,P,{c})
k
10.55
It follows that the (n+1) independent thermodynamic forces can be taken to be the set
T, which measures the local deviation from thermal equilibrium, P, which measures
the deviation from mechanical equilibrium, and the n-1 gradients k, which measure
that part of the deviation from chemical equilibrium that is independent of thermal and
mechanical equilibrium.
10.5.2 The non-equilibrium fluxes and the kinetic equations
The differential volume elements within a non-equilibrium solid can exchange
heat and atomic species. Hence the evolution toward equilibrium is characterized by the
n+1 fluxes: J Q , the heat flux, and J k (k = 1,...,n), the molar fluxes of the n chemical
components.
In the most general case the values of the non-equilibrium fluxes depend on all of
the non-equilibrium forces. The reason is that the flows tend to couple to one another.
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For example, atoms have vibrational energy, and hence transport thermal energy, or heat,
when they diffuse down a temperature gradient. Therefore the heat flow is affected by
gradients in the chemical potential. Since atoms are more mobile at high temperature,
atom diffusion is enhanced if the temperature decreases in the direction of atom flow
since there is less counterflow from random movements of atoms in the colder region;
hence chemical diffusion is affected by a temperature gradient. The diffusional flows of
different chemical species influence one another, particularly when the chemical species
are substitutional solutes that occupy the same crystal lattice, or when one of the species
is so highly mobile that it can transfer momentum to another by collision and help it to
move. The most general form of the kinetic equations for a cubic or isotropic material
can, therefore, be written
n-1
J Q = - LQQT - LQPP -
LQkk
10.56
k=1
n-1
Jk
=-
LkQT
LkPP
Lkk'k'
10.57
k'=1
where there is one equation of the form 10.57 for each independent chemical component.
The coefficients, Lij , are numbers because of the material symmetry, and are material
properties.
10.5.3 Simplification of the kinetic equations
It is, of course, extremely difficult to analyze a process that involves all of the
coupled flows that appear in equations 10.56-57. Fortunately the kinetic equations can be
simplified substantially in most cases of interest. A major reason is the kinetic hierarchy
of the processes that lead to equilibrium. The kinetic hierarchy is such that mechanical
equilibrium is ordinarily established very quickly, thermal equilibrium is achieved in a
reasonably short time, and chemical evolution is relatively slow.
Mechanical equilibrium
A pressure gradient in a solid that is otherwise unconstrained is relaxed by small
displacements of the lattice that happen at the speed of sound. Hence a disturbance in the
mechanical equilibrium of a solid is ordinarily removed in a time that is short compared
to the time needed to reach thermal or chemical equilibrium.
However, the pressure is not always constant when a material is in mechanical
equilibrium.. A more complete analysis of mechanical equilibrium in solids shows that if
balanced, non-uniform forces are applied to the boundary of a solid, it develops an inhomogeneous elastic stress in which the pressure can vary from point to point. The
inhomogeneous stress causes stress-induced diffusion of the chemical species that is
important in many material processes.
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The analysis of stress-induced diffusion is beyond the scope of this course. We

shall confine the following discussion to thermochemical processes at constant pressure.
In this case the governing equations reduce to the set
n-1
JQ
=-
LQQT
LQkk
10.58
k=1
n-1
J k = - LkQT -
Lkk'k'
(k = 1,...,n)
10.59
k'=1
Equations 10.58-59 are a set of n+1 equations for the fluxes J Q and J k (k = 1,...,n)
that involve only the n independent variables T and k (k=1,...,n-1). However, when
the pressure is constant in a material process the fluxes J Q and J k are related to one
another by the requirement that the net flow leave the pressure unchanged. The exact
nature of the mathematical relationship depends on the process and the boundary
conditions that are imposed on the surface of the material, but has the consequence that
one of the fluxes can be found from the others. Using this result to eliminate the nth
chemical flux, J n , equations 10.59 reduce to the set
n-1
J k = - LkQT -
Lkk'k'
(k = 1,...,n-1)
10.60
k'=1
Thermal equilibrium; heat conduction

Since heat can be conducted much more rapidly than atoms can move, thermal
gradients in a solid ordinarily disappear in a time that is short compared to the time
required for any significant chemical change. In this case thermal equilibrium is established by heat conduction alone, and chemical equilibrium is reached by chemical
diffusion at essentially constant temperature. The kinetic equations 10.58-60 then
decouple to read
J Q = - kT
10.61
n-1
Jk
=-
Lkk'k'
(k = 1,...,n-1)
10.62
k'=1
Equation 10.61 is just Fourier's Law of heat conduction, and we have replaced the kinetic
coefficient LQQ by the normal symbol, k, for the thermal conductivity.
It should be noted, however, that the heat and chemical fluxes cannot always be
decoupled. The most important exception is when a temperature gradient is imposed
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externally, as when the opposing surfaces of a solid are held at different temperatures.
Even in this case it is usually possible to neglect the chemical contribution to heat flow,
which is small compared to that due to thermal conductivity. However, the temperature
gradient ordinarily has a significant effect on the chemical flux; its contribution is known
as thermal diffusion. In this case equations 10.60 govern chemical diffusion.
Chemical equilibrium; diffusion

The slowest of the processes involved in the evolution toward internal equilibrium
are the chemical redistributions that lead to chemical equilibrium. Given thermal equilibrium, mass diffusion is described by the kinetic equations gathered in equation 10.62,
where the number of independent equations is one less than the number of components.
In a binary solution only two species are present. There is only one relative
chemical potential, B, which refers to the specie, B, chosen as the solute, and only one
independent diffusion flux, J B , which, still assuming that the solid is isotropic or cubic, is
governed by the constitutive equation
J B = - LBB
10.63
The kinetic coefficient, LB, is called the mobility. Like any other material property of a
binary solution the mobility depends on the nature of the solution, including the identity
of the solvent and the phase, and on the thermodynamic state, which is specified by the
temperature, pressure and composition, LB = LB(T,P,c). For reasons we shall discuss
below the dependence on the temperature is exponential
B
LB = L0 e
Q
- kT
10.64
where Q is the activation energy for diffusion.

We shall restrict our discussion of diffusion in the solid state to the binary case
described by equation 10.63, both because it is the simplest case and because it provides
an adequate description of most of the chemical redistributions that occur in materials.
Even when a solid has several mobile components it is often possible to treat its chemical
evolution as a sequence of binary diffusion processes. The reason is that the different
solute species usually have very different mobilities. The mobility of the fastest-moving
specie is often so much greater than that of the next-fastest that the former can be
assumed to evolve into an equilibrium distribution before the latter redistributes at all.
When this is true the redistribution of the most mobile component occurs against the
background of an almost fixed distribution of the other species, and is, hence, binary
diffusion. As the slower component diffuses, the distribution of the more mobile
component simply evolves with it to preserve equilibrium, so the diffusion of the slower
component can be treated as a binary diffusion problem as well.
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10.6 DIFFUSION
10.6.1 Fick's First Law for the diffusion flux
The equations that govern chemical diffusion in a binary solution at constant temperature and pressure can be written so that they are mathematically identical to those
which govern the conduction of heat (Section 10.2). As shown in Chapter 7, the relative
chemical potential of the solute (specie B in the A-B solution) is the compositional
derivative of the molar Gibbs free energy,
B = c [g(T,P,c)] = B(T,P,c)
10.65
where we have used the symbol c for the concentration of B, and noted that the value of
B is determined by the variables (T,P,c) if g is. The gradient of the relative chemical
potential at constant T, P is
B
B = c c
10.66
that is, it is simply proportional to the concentration gradient. When equation 10.66 is
substituted into equation 10.63, the result is
J B = - nDB c
10.67
where n is the total number of atoms (or moles) per unit volume and the coefficient, D, is
a material property that is called the diffusivity, and is related to the mobility by the
equation
1B
DB = n c LB
10.68
and it follows from equation 10.64 that its temperature dependence is governed by an
exponential relation of the form
B
DB = D0 e
Q
- kT
10.69
Equation 10.69 is known as Fick's First Law. It states that the diffusion flux of
the solute is proportional to the negative of its concentration gradient. Note that Fick's
First Law is valid under three assumptions: (1) the material is a binary solution (or
behaves like a binary solution in the sense discussed in the previous section), (2) the
temperature and pressure are constant, (3) the material has isotropic or cubic symmetry.
If the material does not behave as a binary solution then the diffusion fluxes interact and
equations 10.62 must be used. If the temperature and pressure are inhomogeneous then
terms in T and P must be included in the kinetic equations. When the symmetry of
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the material is not isotropic or cubic then the diffusivity depends on the direction in the
material and the diffusion flux is not generally parallel to the concentration gradient.
10.6.2 Fick's Second Law for the composition change
The change in composition with time can be found by applying the same
reasoning that was used to obtain equations 10.4 and 10.10 for the change in the
temperature with time. First consider a one-dimensional diffusion flow as shown in Fig.
10.6.
The rate of change in the quantity of component B in the central cell in Fig. 10.6
is
NB
B B
t = J12 - J23 dA
10.70
where dA is the interface area. If dx is the length of the volume element, dV2, of the central cell then
JB
B
B
J23 = J12 + x dx
10.71
JB
NB
dV
=
x
t
10.72
So that
Since the volume element, dV, is constant, equation 10.72 can be re-written
JB
nB

=
x
t
10.73
Substituting in the one-dimensional form of Fick's First Law, equation 10.67, yields the
equation
nB
B c
=
t
xnD x
JB
JB
23
12
c1
10.74
c2
Fig. 10.6: Binary diffusion in one dimension.

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If the total atom or molar density, n, is constant during diffusion then both sides
of equation 10.74 can be divided by n to obtain the simpler diffusion equation
c
Bc
=
t
xD x
10.75
By its definition the diffusivity is a material property that is a function of T, P and c.

Since T and P are constant by assumption,
DBc
DB
=
c x
x
10.76
and equation 10.75 can be written

2c DBc 2
c

B
=
D
x2 + c x
t
10.77
which is a partial differential equation for the concentration field, c(x,t). When the
dependence of the diffusivity on the composition can be ignored the composition is
determined by the simple equation
2c
c
B
=
D
x2
t
10.78
which is an example of the diffusion equation like the governing equation for the
temperature, eq. 10.10. Equation 10.78 is called Fick's Second Law.
Fick's Second Law is a valid equation for the concentration, c(x,t), when Fick's
First Law (eq. 10.67) applies, and when, in addition, the total atom density is constant
and the diffusivity is independent of concentration. These conditions are often satisfied
to a reasonable approximation. The total atom density is essentially equal to the total
number of atom sites per unit volume; when the solution is substitutional the number of
vacancies is always small, and when the solution is interstitial the number of interstitial
atoms is almost always small. Since the pressure is constant the number of atom sites is
nearly constant unless the volume per site is a strong function of the composition. This is
the case when the two components have very different atomic volumes. An equation like
10.78 holds even then, but with a multiplying constant on the right-hand side. The
diffusivity becomes a strong function of composition when the solute concentration is
high and the two components have very different atomic volumes, since the lattice is then
distorted to an extent that depends on the concentration. In this case equation 10.78
governs the evolution of the concentration and the mathematical analysis of diffusion is
much more difficult.
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10.6.3 Solutions of the diffusion equation

A thorough discussion of the solutions to the diffusion equation is beyond the
scope of this course. However, it is useful to know the solution for a few simple
situations that be used as reference cases to help understand material behavior. The onedimensional diffusion equation, 10.78, has simple solutions in each of the cases shown in
Fig. 10.7.
(a)
(b)
(c)
Fig. 10.7: Three examples of diffusion in one dimension. (a) A thin slab
(point source) of B is embedded in an infinite bar of A and allowed to diffuse. (b) Semi-infinite bars of A and B are joined
together and allowed to interdiffuse. (c) B is plated on the surface of A and allowed to interdiffuse.
First, let a thin slab of element B be located in the interior of an essentially
infinite bar of material A, as shown in Fig. 10.7(a). If the total number of moles of B is
NB, and the slab is located at x = 0, the concentration of B as a function of position and
time is given by the equation
c(x,t) =
NB
2 Dt
x2
exp- 4Dt
10.79
One can verify by direct substitution that eq. 10.79 is a solution of the differential
equation, 10.78, and satisfies the constraint
c(x,t)dx = NB
10.80
which insures that the total quantity of B is the same at all times. The concentration field
has a simple Gaussian form, and develops with time as shown in Fig. 10.8.
Second, let a semi-infinite bar that has composition, c0, of B in A be brought into
contact with a semi-infinite bar of pure A, as shown in Fig. 10.7(b). Let the interface be
at x = 0. The total quantity of B per unit area perpendicular to the axis of the bar at
position x' < 0 is c0dx'. According to eq. 10.79, this increment of material makes a
contribution
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c(x,t) =
(x-x')2
exp- 4Dt
c0dx'
2 Dt
10.81
to the concentration at position x at time t. If we change the variable on the right-hand

side of eq. 10.81 from x' to = (x-x')/2 Dt , and integrate over the range of that
corresponds to - < x' < 0, the result is
c0
x
c(x,t) = 2 erfc
2 Dt
10.82
where the symbol erfc() stands for the "complementary error function", which is defined
by the integral
z
2
exp[- 2] d
erfc(z) = 1 0
10.83
The complementary error function is tabulated in standard math tables. It has the limiting
properties
erfc(0) = 1
erfc() = 0
erfc(-z) = 2 - erfc(z)
10.84
concentration
t1
t2
t3
distance
Fig. 10.8: The development of the concentration profile with time for
one-dimensional diffusion from a point source (Fig. 10.7(a)).
The development of the concentration field as a function of diffusion time is illustrated in Fig. 10.9. Note that the concentration at x = 0 is fixed at the value c0/2.
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concentration
t1
t2
t3
distance
Fig. 10.9: The development of the concentration profile with time for
one-dimensional diffusion in the geometry shown in Fig.
10.7(b).
Third, consider the diffusion of B from the surface into a semi-infinite body of A.
There are two relevant cases. In the first, a quantity, NB, of B is plated onto the surface
and allowed to diffuse in. In the second, the environment is controlled so that the
concentration of B at the surface is maintained at a fixed value. For a fixed quantity of B,
eq. 10.79 applies. We can solve the problem by, effectively, slicing Fig. 10.7(a) in half.
The result is
c(x,t) =
NB
Dt
x2
exp- 4Dt
(x 0)
10.85
The concentration field is shown as a function of time in Fig. 10.10(a). For a

fixed concentration, c0, of B, eq. 10.82 applies. For positive x this equation yields a
solution to the diffusion equation that has a fixed, constant concentration on the boundary
at x = 0. Setting this concentration at c0, we have
x
c(x,t) = c0erfc
2 Dt
10.86
the development of the concentration field is illustrated in Fig. 10.10(b).
concentration
concentration
t1
t2
t3
t1
t2
t3
distance
distance
(a)
(b)
Fig. 10.10: Concentration profiles for diffusion from a surface with: (a)
fixed quantity of deposit; (b) fixed concentration.
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10.7 THE MECHANISM OF DIFFUSION IN THE SOLID STATE

10.7.1 The mobility of interstitial species
With very few exceptions atoms in solids diffuse by discrete jumps from one
atom site to another. The jumping process is easiest to visualize when the diffusing atom
is interstitial.
Fig. 10.11 is a two-dimensional drawing of an interstitial atom in a square lattice.
The atom moves by jumping to one of the closest interstitial sites. However, the atom is
held in its initial position by the surrounding lattice atoms, and can only move if these are
displaced as shown in the upper right-hand figure. Any such displacement increases the
free energy of the system. The change in free energy as the interstitial atom is displaced
from one equilibrium position to another is diagrammed in the figure. The maximum
free energy increment during the displacement is Gm, as shown in the figure. Gm is
called the activation free energy for atom motion.
If the atoms were quiescent then the interstitial atom could only move if the
activation energy were supplied from some external source. However, the atoms in a
solid are in constant thermal agitation. At normal temperatures they oscillate about their
equilibrium positions with a frequency of about 1013 per second (the Einstein frequency
). With each oscillation the interstitial atom approaches the barrier of lattice atoms that
separates it from a neighboring interstitial position. If the vibrations of the lattice atoms
are such that their instantaneous configuration is like that shown in the upper right in Fig.
10.11 then the atom can pass through to the neighbor site.
Gm
x
Fig. 10.11: An interstitial atom in a square lattice moves from site to site
through intermediate configurations like that shown at upper
right. The associated free energy change is diagrammed at
lower right.
If a system whose temperature, pressure and composition are fixed has Gibbs free
energy, G, then the probability that it will sample an excited state of free energy G + G
in a single trial is
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P(G) e
- G
kT
S/k
=e
- H
kT
10.87
where we have used the relation G = H - TS. The thermal dependence of the probability is governed by the enthalpy change, H. The number of jumps per unit time ()
that the interstitial atom of Fig. 10.7 makes to nearest neighbor sites is, therefore, equal to
the number of trials multiplied by the probability of success per trial, or
= e
Qm
kT
10.88
where the effective frequency, , is

Sm/k
= z0e
10.89
In this last expression z is the number of nearest neighbor interstitial sites (which are assumed separated by identical activation barriers), 0 is the frequency of atom vibration,
Gm = Hm - TSm, and Qm = Hm is the activation energy for migration.
The effective frequency, , is about 1014 per second in a typical cubic solid. The
activation energy for migration of an interstitial depends on the nature of the interstitial
and the lattice, but is usually of the order of 1 eV, which is the value of kT at about 104
K. It follows that at 500 K (223 C) an interstitial atom makes about 105 site-to-site
jumps per second.
10.7.2 The mobility of substitutional species
While a lattice vacancy moves from site to site very much as an interstitial atom
does, a substitutional atom can only jump to a neighboring site if that site is vacant.
Hence the rate of diffusion of a substitutional specie depends strongly on the
concentration of vacancies. Even when a vacant site is available for a substitutional atom
jump, the jump is still complicated by two effects.
First, there is an activation barrier (Gm) opposing the jump. One source of the
activation barrier is illustrated in Fig. 10.12, which shows a two-dimensional closepacked group of atoms including a vacancy. As shown in the figure, the central atom can
only move into the vacancy if its neighbors "open up" and allow it through. The open
configuration is a non-equilibrium configuration with a free energy Gm above that of
the ground state.
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(a)
(b)
...
Fig. 10.12: Mechanism of diffusion of a substitutional atom: (a) substitutional atom with a neighboring vacancy (shaded); (b)
neighboring atoms "open up" to let the atom move into the
vacancy.
Second, only some of the atom-vacancy exchanges actually contribute to
diffusion. Immediately after a substitutional atom has exchanged positions with a
vacancy, as in Fig. 10.12, the vacancy is in the particular neighbor site that would reverse
the atom jump that had just been performed. There is, therefore, a higher than random
probability that the next atom jump will simply cancel the previous one so that both
jumps are ineffective. This phenomenon is known as the correlation effect in the
diffusion of substitutional species. When the lattice atoms have roughly equal
probabilities of exchanging with the vacancy the correlation effect is not large. For
example, an atom site in an FCC structure has twelve nearest neighbors. If the vacancy is
equally likely to exchange with any one of its neighbors then the probability that an atom
jump will be reversed by the succeeding jump is only 1/12. Even if we include the
possibility that a jump is reversed after two or more atom exchanges with the vacancy the
correlation effect remains small. Hence. we ordinarily ignore the correlation effect when
we are concerned with the self-diffusion of the lattice specie in a one-component solid or
the diffusion of a substitutional solute that is similar in size to the solvent specie.
Correlation effects can be important when the different components of a substitutional
solution have significantly different activation energies for exchanging with a vacancy.
We shall not consider such cases here.
The jump frequency of a substitutional atom is the product of two terms: the jump
frequency into vacant neighbor sites, and the probability that a neighbor site is vacant to
accept the jump. If the vacancies are randomly distributed the probability that a neighbor
site is vacant is just cv, the atom fraction of vacancies, and
= cv e
Qm
kT
10.90
where is the effective frequency (eq. 10.89) and Qm is the activation energy for migration. As shown in Chapter 8, the equilibrium vacancy concentration, cv, is
cv = Ae
QV
kT
10.91
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where A is a pre-exponential factor and Qv is the energy of formation of a vacancy.

When the vacancy concentration has its equilibrium value the jump frequency is
= Ae
Q
- kT
10.92
where Q, the activation energy for an atom jump, is

Q = Qv + Qm
10.93
the sum of the activation energy to form a vacancy and the activation energy for atom exchange with a vacancy. These activation energies vary significantly from material to
material, but both are of the order of an electron volt. Hence the effective activation
energy that governs the jump of a substitutional atom is of the order of twice that for an
interstitial atom.
Equation 10.92 is adequate to understand the mechanism of diffusion of a
substitutional specie, but should be modified in at least two respects for quantitative
accuracy. First, because of the correlation effect a larger than random fraction of the
atom jumps of a substitutional specie are reversed and do not contribute to diffusion. The
effective frequency of diffusional jumps is, therefore,
eff = f
10.94
where the factor f accounts for correlation. Second, the vacancy concentration that
appears in the jump frequency is, strictly, the vacancy concentration at a site adjacent to
the atom that performs the jump. If the atom has a strong interaction with vacancies then
the activation energy, Qv, for forming a vacancy may change significantly. Even when
these changes are important, however, the effective jump frequency is given by an
equation of the form of equation 10.92 with an activation energy of the form 10.93.
10.7.3 Random-walk diffusion; Fick's First Law
The individual jumps of the atoms within a uniform solid are random in direction.
Over time an atom experiences a sequence of such jumps and meanders through the solid
in an aimless path known as a random walk. But even though the individual atoms
wander aimlessly through the solid there is a net diffusional transport of matter when the
composition is non-uniform. The reason is that a random walk of the atomic species
creates a more random, or uniform overall distribution and gradually smoothes
compositional heterogeneities. An analysis of random-walk diffusion reveals the
connection between the jumps of the individual atoms and the macroscopic diffusivity
that is defined by Fick's First Law.
For example, consider a solid with a simple cubic structure that is uniform except
for a concentration variation in the [100], or x-direction. The diffusional flux in the x-
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direction is the net flow of atoms per unit area across a plane perpendicular to x, which is
the net flow between adjacent (100) planes.
J21
J12
a
c2
c1
Fig. 10.13: Diffusion between adjacent (100) planes in a simple cubic

crystal.
Fig. 10.13 shows three adjacent unit cells of a simple cubic crystal that abut in the
x-direction. The net flow of solute atoms per unit area between adjacent (100) planes
(which are labeled 1 and 2 and shaded in the figure) is the net flux across a plane midway
between them. Hence
J = J12 - J21
10.95
where J12 is the flow per unit area from plane 1 to plane 2 and J21 is the counterflow
from 2 to 1. The flow is due to atom jumps in the x-direction. Let the frequency with
which a solute atom jumps in the positive x-direction be x. Then
J12 = n1x
10.96
where n1 is the number of solute atoms per unit area of plane 1.

concentration on plane 1 is c1 then
n1 = nc1a
If the solute
10.97
where n is the number of atom sites per unit volume and the volume per unit area of plane
is equal to the interplanar spacing, a. If the solute concentration is a continuous function
of x that varies only slightly between planes 1 and 2,
c
c2 = c1 + x a
10.98
If an atom is equally likely to exchange with each of its six neighbor sites in the simple
cubic structure,
x = 6
10.99
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where is the effective frequency of solute atom jumps per unit time. Writing an
equation like 10.96 for the counterflow, J21, and using eqs. 10.97=99, the net flux is
c
1
1
J = 6 a(c1 - c2) = - 6 a2x
10.100
Equation 10.100 has the one-dimensional form of Fick's First Law,

c
J = - nDx
10.101
1
D = 6 a2
10.102
with the diffusivity,
It can be shown that equation 10.102 holds in general for materials with cubic
structures. The parameter, a, is the length of the elementary atom jump. It is the interatomic distance for substitutional diffusion, and the distance between neighboring
interstitial sites for interstitial diffusion. Equation 10.102 provides the connection
between the frequency of atom jumps and the diffusivity. It follows that the diffusivity
can be written
QD
D = D0 exp- kT
10.102
where the activation energy for diffusion, QD, is equal to Qm for the diffusion of
vacancies or interstitial atoms, and is equal to Qm+Qv for the diffusion of substitutional
species in a solid that has an equilibrium vacancy concentration.
10.7.4 The mean diffusion distance in random walk diffusion
Further useful insight into the mechanism and consequences of random-walk diffusion can be garnered from an analysis of the mean diffusion distance. If an atom
diffuses by performing a random walk in a homogeneous solid then its position after time
t is displaced by the vector X from its initial position, as illustrated by the example in Fig.
10.14. Since the net displacement, X, is equally likely to lie in any direction its expected
value, X, is zero at all times. However, it is very unlikely that the atom will be found in
its initial position after it has performed many jumps. The expected value of the mean
diffusion distance, XD, should not be zero, and should increase with the number of atom
jumps.
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...
Fig. 10.14: The random walk of an interstitial atom causes a net
displacement, X, in time t.
The mean diffusion distance is the expected value of the magnitude, |X|, of the
displacement, X, independent of its direction. Hence
XD = |X| = X^X
10.103
where X^X is the mean square displacement, the expected value of the scalar product
of the displacement vector with itself. The mean square displacement is relatively easy to
compute for a cubic solid with random atom jumps. Let a i be the ith jump in the
sequence of the n jumps an atom makes in the time, t. Assuming that all jumps are to
nearest neighbor positions, all jump vectors have the same magnitude, a, where a is the
distance to the nearest neighbor site. They differ only in direction. The total
displacement vector, X, is the vector sum of the vector displacements in the n elementary
jumps:
n
X=
ai
10.104
i=1
Hence
n
X^X =
a i â j
i=1 j=1
n
k=1
a i â i +
a i â j
10.105
i=1 ji=1
The first summation on the right in this last expression includes the terms in which the
two jumps are the same while the second includes all terms that involve the scalar
product of the ith jump vector and the jth when j i. If there are many jumps in the sequence the expected value of the second term on the right in 10.105 is zero; the jump a j
is equally likely to be in the negative as the positive direction, so the terms in the series
cancel one another in pairs. Since a i â i = a2 the value of the first sum is just na2, so
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X^X = na2 = a2t
10.106
where is the effective number of atom jumps per unit time. The mean square displacement is the sum of the mean square displacements in the three coordinate directions:
X^X = (xe x + ye y + ze z )^(xe x + ye y + ze z )
= x2 + y2 + z2 = 3x2
10.107
where x, y and z are the displacements in the three coordinate directions. In a cubic solid
the mean square displacements in the three coordinate directions are equal, so
1
x2 = 3 a2t
= 2Dt
10.108
where D is the diffusivity, D = a2/6.

Since all directions are the same for diffusion in a cubic solid equation 10.108
gives the mean linear diffusion distance
xD = 2Dt
10.109
which measures the expected linear displacement of an atom that has diffusivity, D, after
a random walk for time t.
10.7.5 Uses of the mean diffusion distance
Equation 10.109 is a very useful relation. The two most common situations in the
practice of materials science in which it is desirable to know the kinetics of diffusion are
in the processing of materials, where it is important to know the time required to
complete a diffusional process, and in the use of chemically heterogeneous materials,
where it is important to know that diffusion will not significantly disturb the chemical
heterogeneity during the expected service life of the material. In both cases it is often unnecessary to know the detailed evolution of the concentration; what is needed is a rough
estimate of the time required for the relevant diffusion process to occur. This estimate
can often be made directly from equation 10.109, as illustrated by the following two
examples.
Time required to homogenize a heterogeneous material

The first example is the homogenization of a freshly solidified material with an
inhomogeneous distribution of solute. For reasons we shall discuss below, when a multicomponent solid is cast from the liquid its composition is usually inhomogeneous even
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when its microstructure contains only a single phase. The compositional heterogeneity
develops because solidification occurs gradually on cooling through the two-phase
region, and is a roughly periodic variation about the mean concentration, c, as illustrated
in Fig. 10.15. The compositional heterogeneity is eliminated by giving the material a
homogenization treatment in which it is heated to the highest practical temperature and
held for a time long enough for the concentration to become uniform.
Fig. 10.15: Inhomogeneous concentration profile after solidification.

To estimate the time required to homogenize a material we note that the peaks and
valleys that appear in the composition profile will certainly disappear if the material is
held at temperature for a time long enough that the linear diffusion distance, xD, is large
compared to the peak-to-valley distance, /2, where is the effective wavelength of the
composition. The material should homogenize in a time of the order
2
t > th = 8D
10.110
Since the diffusivity varies exponentially with the temperature, equation 10.110 can be
used to select a temperature at which homogenization is completed in a practical time.
Eq. 10.110 also reveals when th is impractically long at all reasonable temperatures (as it
is, for example, for many alloys that are potentially useful in high-temperature structures)
in which case some alternative to conventional homogenization must be found.
Service life of a chemically heterogeneous material

A second important example occurs in semiconducting devices. As we shall discuss at a later point in the course, these devices usually consist of silicon crystals, or
chips, whose surfaces are "doped" locally with selected solutes to control their electrical
characteristics, as illustrated in Fig. 10.16. Silicon chips are, hence, non-equilibrium
structures with implanted compositional heterogeneities. The moment the doping is
completed the heterogeneity begins to diffuse away.
P
Si
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Fig. 10.16: An Si crystal locally doped with P to the depth .

The maximum possible service life of the chip is limited by the diffusion time of
the dopant. Assuming a device depth, , the service time, ts , and the service temperature
must be such that
2
ts << 8D
10.111
This requirement is relatively easy to satisfy when the chip is kept cool, but can become a
limiting problem when is very small and the device is heated by the environment or by
the current developed during operation.
10.8 MICROSTRUCTURAL EFFECTS IN DIFFUSION

The diffusivity of an atom is strongly affected by the composition and structure of
the material in which it appears. The diffusivity is also affected by other aspects of the
microstructure, such as grain boundaries, dislocations, and point defects. The microstructural effects are most pronounced when the diffusing specie is substitutional.
10.8.1 The vacancy concentration
The diffusivity of a substitutional component is proportional to the vacancy
concentration, cv. The vacancy concentration can be significantly changed, at least in a
transient sense, by cooling the material from high temperature, by deforming it, by
bombarding it with radiation, or by adding solutes that promote vacancy formation.
Quench-enhanced diffusivity
The equilibrium vacancy concentration is an exponential function of the temperature. If a material is brought into equilibrium at high temperature and then cooled
quickly, the high-temperature vacancy concentration is preserved for some time; the
excess vacancies must diffuse to boundaries, dislocations or other sinks before they can
be eliminated. Consequently the diffusivity of a substitutional species is anomalously
high immediately after a quench. It decreases gradually to the equilibrium value as
illustrated in Fig. 10.17. The plot given in Fig. 10.17 is on a semi-logarithmic scale since
the initial vacancy concentration, and hence the initial diffusivity, is raised by several
orders of magnitude if the material is quenched from high temperature.
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ln(D)
Deq
...
Fig. 10.17: Schematic drawing of the variation of the diffusivity of a
substitutional specie with time after a quench. Deq is the
equilibrium value of D at the final temperature.
Quench-enhanced solute diffusivity is often useful in materials processing.
Processes such as precipitation in the solid state are sluggish at the low temperatures at
which it is often desirable to make them happen. Their rates can be increased by
quenching from high temperature.
Deformation-enhanced diffusivity
The diffusivity of a substitutional component is increased by concurrent plastic
deformation. The motion of dislocations in plastic deformation always involves at least
some dislocation climb, which produces vacancies. The diffusivity is raised accordingly.
Concurrent plastic deformation may also increase the diffusivity of very mobile
interstitial species such as hydrogen. Interstitial species tend to accumulate near
dislocations that have some edge component because the lattice beneath the extra halfplane of an edge dislocation is expanded and can better accommodate interstitial defects.
The excess solute is said to form a solute atmosphere about the dislocation. If the
interstitials are sufficiently mobile they remain with the dislocation when it moves. This
process, which is known as dislocation sweeping, is a significant source of hydrogen
diffusion in solids that are deformed at low temperature.
Irradiation-enhanced diffusivity
Irradiation substantially enhances diffusivity by increasing the density of point defects. Intense radiation knocks atoms off of their lattice sites to create vacancyinterstitialcy pairs. The vacancies increase diffusivity on the lattice while the interstitials
are mobile through the interstitial sites. The enhanced diffusivity of irradiated solids is
sometimes useful in materials processing, but accelerates the degradation of materials
used in nuclear devices.
Solute-enhanced diffusivity
Solute atoms may increase the concentration of vacancies by lowering their
energy. Important examples include solutes of relatively large atomic volume, which
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promote the formation of vacancies on adjacent sites to minimize the net lattice strain,
and solutes of different ionic charge in ionic solids, which promote the formation of
vacancies to reestablish charge neutrality. An example of the latter is Mg in NaCl; Mg++
ions are balanced by Na+ vacancies, which raise the diffusivity of Na.
10.8.2 Grain boundary diffusion
If the material is polycrystalline, substitutional solutes can diffuse along the
continuous network of grain boundaries as well as through the bulk of the crystal. A
grain boundary is a region of disorder where adjacent crystals do not fit perfectly
together. To a first approximation the grain boundary can be pictured as a region of
distorted crystal that contains a very high density of vacant sites. The grain boundary
diffusivity obeys an equation that is of the form
QB
B
DB = D0 exp- kT
10.112
where QB is of the order of one-half the activation energy for diffusion through the bulk,
QD, reflecting the fact that it is not usually necessary to form a vacancy to accomplish an
atom jump.
B
The pre-exponential factor, D0 , for grain boundary diffusion is also much

smaller than D0 for diffusion through the bulk. To understand why, recall that the
diffusivity governs the net flux of atoms across a cross-sectional plane through the solid.
The flux due to grain boundary diffusion is restricted by the small areal fraction of grain
boundary on a cross-section through the material.
Consider a solid with cubic grains of size, d, whose grain boundaries have an effective width, , as drawn in Fig. 10.18. The cross-sectional area per grain is d2 and the
cross-sectional area of grain boundary per grain is 4d(/2); the fractional area of grain
boundary in a cross-section is proportional to (/d). If the activation energy for diffusion
in both parts of the microstructure were the same the flux would be proportional to the
relative cross-section. Hence
B
D0 D0d
10.113
Since is of the order of a few , while d is typically of the order 104-106 ,

B
D0 << D0
10.114
Atoms diffuse simultaneously through the bulk and along the grain boundaries, so
these provide parallel diffusion paths. The net diffusion flux is the sum of the flux each
contributes. The ratio of the two diffusivities is
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B
(Q-QB)
DB
D0
=
exp
kT
D0
D
10.115
When the temperature is very large the exponential term approaches 1 and DB << D.
Hence at high temperature almost all of the flux is due to bulk diffusion. As the
temperature approaches zero, however, the exponential term becomes arbitrarily large
since Q > QB. At sufficiently low temperature, DB >> D, and the flux is almost
exclusively along the grain boundaries.
Fig. 10.18: Section through a microstructure of square grains whose

grain boundaries have effective width, .
The variation of the effective diffusivity with temperature is sketched
qualitatively in Figure 10.19. Since
Q
ln(D) = ln(D0) - kT
10.116
a plot of ln(D) against (1/kT) is a straight line with slope -Q that approaches ln(D0) in the
limit T (T-1 0). The total diffusivity is determined by the greater of the bulk and
grain boundary diffusivities. The effective diffusivity is given by two straight lines that
join at the temperature at which the dominant mechanism of diffusion changes, as shown
in the figure.
B
The value of D0 increases as the grain size becomes smaller. Hence the grain
boundary diffusivity and the temperature at which it becomes dominant increase as the
grain size decreases as shown in the figure.
A particular case in which grain boundary diffusion is important is in the selection
of diffusion barriers to separate reactive species at low temperature. This is a
particularly important problem in microelectronics. Microelectronic devices usually
contain dissimilar materials in intimate contact, such as metallic conductors in contact
with silicon or oxide insulators. Because of the extremely small dimensions of the
individual material elements and the sensitivity of their electrical properties, chemical
reactions can be a problem even at very low temperature. Thin films of very stable
materials are, therefore, often inserted as diffusion barriers to separate reactive materials
from one another. An effective diffusion barrier must be such that both reactive species
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diffuse very slowly through it. However, the diffusion barriers are deposited films and
are almost always polycrystalline.
At the low temperature of operation of
microelectronic devices grain boundary diffusion usually predominates, so diffusion
barriers must be selected on the basis of the grain boundary diffusivities rather than the
bulk diffusivities of the species to be separated.
D0
ln(D)
DB
0
decreasing
grain size
-QD
-QB
1/kT
...
Fig. 10.19: Semi-logarithmic plot of diffusivity against reciprocal
temperature for a polygranular material. The grain boundary
diffusivity increases as grain size decreases as shown.
10.8.3 Diffusion through dislocation cores

Diffusion is also easier along the core of a dislocation that has at least some edge
component. Interstitial species move more easily through the expanded lattice below the
dislocation (that is, below the termination of the extra half-plane), and substitutional
species are more mobile in the compressed lattice above the dislocation since vacancies
have lower energy there. However, excepting the case in which planar arrays of
dislocations form low-angle grain boundaries, dislocation cores fill a negligible fraction
of the cross-section of a crystal. Diffusion along dislocation cores is rarely important
except at very low temperature in materials that have been severely deformed to create a
very high dislocation density.
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Chapter 11: Phase Transformations

After conquering Sardis, capital of Lydia and wealthiest city in the world, the Persian
King Cyrus the Great had the captured Lydian King, Croesus, brought to him ...
For a while Croesus was deep in his thoughts and did not speak.
Then he turned and, seeing that the Persians were sacking the town, said,
"Should I tell you, my lord, what I have in my mind, or must I now keep
silent?" Cyrus replied that he might say what he pleased without fear, so
Croesus put another question: "What is it," he asked, "that all those men
of yours are so intent upon doing?"
"They are plundering your city and carrying off your treasures."
"Not my city or my treasures," Croesus answered. "Nothing here
any longer belongs to me. It is you they are robbing."
-Herodotus, "The Histories"
11.1 COMMON TYPES OF PHASE TRANSFORMATIONS

A phase transformation is a discontinuous change in the microstructure of a material. Phase transformations happen when it is both thermodynamically and kinetically
possible to reconfigure the material so that its thermodynamic potential is lowered. In the
most common case the temperature, pressure and composition are fixed, so the thermodynamic potential that governs equilibrium is the Gibbs free energy. A material can change
its phase if there is an alternate phase with a lower free energy, but it will do so only if
there is a transformation mechanism that can act at a measurable rate.
There are several physically distinct types of phase transformations, including the
following:
1. Structural transformations alter the basic arrangement of atoms in the material.
Familiar examples include boiling and freezing, crystal structure changes such as the
(FCC) to (BCC) phase transition that occurs when iron is cooled, and glass transitions
that "freeze" a rapidly cooled liquid into an amorphous solid state.
2. Recrystallization reactions occur in severely deformed metals, and replace the
deformed grains with new ones that have the same basic crystal structure, but are
relatively free of defects.
3. Ordering reactions change the distribution of atoms over a fixed framework of
atom positions to create an ordered compound. An example is the (disordered BCC) to
' (CsCl) transition in -brass (50Cu-50Zn).
4. Precipitation reactions create second-phase particles within a parent solution to
make a two-phase mixture. The chemical composition of the precipitate is always
different from that of the parent phase, but the basic crystal structure (the arrangement of
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atom sites, irrespective of atom type) may be the same. If it is the same, then the
precipitation reaction may be coherent in the sense that the parent lattice is continuous
across the precipitate interface. An example of a coherent precipitation reaction is the
precipitation of Ni3Al from an FCC solid solution of Al in Ni. If the basic crystal
structure of the precipitate is different from that of the parent then the precipitation
reaction is necessarily incoherent, and the lattice is discontinuous at the precipitate
interface. An example of an incoherent precipitation reaction is the precipitation of Fe3C
from a supersaturated solution of C in Fe.
5. Ferroelectric transitions occur in some ionic solids, and involve spontaneous
ion displacements that create permanent dipole moments. The most frequently cited example is the ferroelectric transition in BaTiO3, which was described in Chapter 9. When
the material is cooled to a temperature below a critical temperature called the Curie
temperature the Ti+4 ions are slightly and spontaneously displaced from the center of the
BaTiO3 unit cell to create a permanent electric dipole.
6. Magnetic transitions occur in materials whose atoms have permanent magnetic
moments. At sufficiently low temperature the magnetic moments spontaneously align
with one another. If the alignment is parallel the transition is called ferromagnetic and
the transition temperature is called the Curie temperature (as described in Chapter 9). If
the alignment is anti-parallel the transition is called antiferromagnetic and the transition
temperature is called the Neel temperature.
7. Electronic transitions are changes in the distribution of electrons that alter the
nature of electrical conduction. Ordinarily electronic transitions change the nature of
bonding in a way that is so fundamental that the crystal structure changes at the same
time. An example is the transition from gray tin, a semiconductor with a diamond cubic
structure, to white tin, a metal with a tetragonal structure, that occurs on heating. In cases
like this the electronic transition can usually be treated as an incidental feature of a
structural transition. However, there are cases in which the electronic structure changes
without altering the crystal lattice. The most spectacular example is the superconducting
transition in which charge carriers spontaneously pair in a nominal metal or
superconductor so that all electrical resistance is lost.
In this chapter we shall concentrate on the phase transformations that change the
structure or chemical distribution. The phase transformation that change the electromagnetic properties of materials will be treated in the discussion of electromagnetic
properties later in the course.
11.2 THE BASIC TRANSFORMATION MECHANISMS

11.2.1 Nucleated transformations and instabilities
While the driving force for a phase transformation at given T and P is a decrease
in the Gibbs free energy, the kinetics of the transformation depend on the mechanism by
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which it is accomplished. It is useful to divide the mechanisms of phase transitions into

two characteristic types: nucleated transitions and instabilities. The distinction is easiest
to see in the case of a monolithic structural transformation in a one-component system.
If the equilibrium of a one-component system places it in the structure at high
temperature and in the structure at low temperature then the free energy curves for the
two phases will ordinarily appear as shown in Fig. 11.1. The free energy curves intersect
at the temperature T0. However, it is usually possible to preserve the structure in a
metastable state at temperatures below T0, as indicated by the extension of its free energy
curve. The driving force, G, for the transformation ordinarily increases as the
temperature is decreased below T0, but, so long as the phase is metastable, the system
must be perturbed in some finite way to cause the transformation to take place.
instability
nucleated
=> metastable
=> equilibrium
T0
T
Fig. 11.1: Free energy curves for hypothetical phases and showing
the range of metastability of , and situations in which
nucleated and instability transitions occur.
The most favorable transformation mechanism is that which requires the smallest
disturbance of the metastable phase. This is usually the formation of a small seed, or
nucleus, of the phase within the body of the . Once a stable nucleus of has formed
then the free energy decreases continuously as the nucleus grows to consume the and
complete the transformation. The nucleation-and-growth process is the usual mechanism
by which a metastable phase transforms. Since nucleation requires a significant (though
local) change in the parent phase, a nucleated transformation can often be suppressed or
delayed by cooling the material at a sufficiently rapid rate.
However, it often happens that the phase cannot be cooled indefinitely. At
some temperature below its equilibrium transformation temperature the phase may
become thermodynamically unstable, either because of internal changes or because the
driving force for the transformation becomes so large that a significant volume of can
transform spontaneously. The limit of stability of the phase is indicated in Fig. 11.1 by
a termination of the free energy curve. The termination defines an instability at which
the phase must transform; a transformation that is due to an instability cannot be
suppressed.
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11.2.2 First-order transitions and mutations

As we discussed in Chapter 9, a phase transition of the type diagrammed in Fig.
11.1 is called a first-order phase transition. A first-order transition connects structures
that are physically different and involves discontinuous changes in at least some of the
thermodynamic quantities. For example, even when the transformation diagrammed in
Fig. 11.1 happens at the equilibrium temperature the entropy changes discontinuously.
Structural transformations are ordinarily first-order as are precipitation reactions and
many of the reactions that create chemical order.
When two phases are related by a first-order transition it is always possible to preserve them in metastable states beyond the equilibrium transformation temperature.
Hence first-order transitions that occur sufficiently near the equilibrium transformation
temperature must be nucleated. On the other hand, the range of metastability of a phase
that participates in a first-order transition may or may not be limited by an instability. In
many cases the metastable phase can be preserved at temperatures as far below the
transition temperature as desired. There is always a nucleation-and-growth mechanism
for a first-order transition. There may also be an instability mechanism, but there need
not necessarily be.
There is a second class of phase transitions, which we have called mutations, in
which two phases that have distinct structures away from the transition temperature
become identical to one another at the transition point. In this case the free energy curves
merge at the transition temperature and metastability is impossible. Effectively, the
stability limit and the equilibrium transition temperature are the same. Such transitions
do not require nucleation; the transformation mechanism is an instability that cannot be
suppressed. These transitions are often called second-order transitions, since the
discontinuity at the transition temperature is not in the thermodynamic quantities, such as
the entropy, but in their derivatives, such as the isobaric specific heat.
Important examples of mutations include glass transitions, in which the liquid and
solid states merge together, ferroelectric transitions, where the ion displacement and,
hence, the induced dipole become imperceptibly small at the Curie point, magnetic transitions, in which the degree of magnetic alignment vanishes at the Curie or Neel points,
and superconducting transitions. As we discussed in Chapter 9, chemical ordering
reactions are sometimes mutations and sometimes first-order phase transitions, depending
on whether the degree of order vanishes continuously at the transition temperature or
changes discontinuously there (the ordering reactions that can be transmutations are
identified theoretically by the Landau symmetry rules, which are beyond the scope of this
course).
11.3 HOMOGENEOUS NUCLEATION

11.3.1 Nucleation as a thermally activated process
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When the parent phase is stable with respect to infinitesimal changes in its local
state (i.e., when it is metastable), the phase transformation must be nucleated if it is to
happen at all. Nucleation is a finite fluctuation in which a small element of the parent
spontaneously takes on a state that is very close to that of the product phase. Since the
spontaneous reconfiguration of a significant volume of stable material is extremely
unlikely, the fluctuations that lead to nucleated transformations are local, and produce
candidate nuclei that are very small. When nuclei form at more or less random positions
within the metastable parent phase the process is known as homogeneous nucleation.
When the nuclei form preferentially at catalytic sites in the parent the process is called
heterogeneous nucleation. We shall consider homogeneous nucleation first.
The thermodynamics of nucleation can be understood by writing the free energy
of the nucleus as the sum of two separate contributions (Fig. 11.2). First, the nucleus
introduces a small volume of product phase. Since this phase is more stable than the
parent phase, the associated free energy change is negative. The formation of the nucleus
also creates an interface between the parent and product phases. The interfacial energy is
necessarily positive, and raises the free energy. The total free energy change is the sum
of the two effects.
Fig. 11.2: A spherical nucleus of phase , surrounded by an interface,

forms within homogeneous phase .
However, the volume and surface contributions to the free energy depend differently on the nucleus size; the surface energy is proportional to the surface area, and hence
to r2, where r is the effective radius of the nucleus, while the volume energy is
proportional to r3. When the nucleus is very small, r2 > r3 and the surface term dominates; the formation of a nucleus raises the free energy. When the nucleus is larger, r3 >
r2 and the volume term dominates; the growth of the nucleus lowers the free energy of
the system if the product phase is thermodynamically stable.
This relationship is illustrated in Fig. 11.3. The free energy change on forming
the nucleus is a function of its size, and passes through a maximum, G*, as the effective
radius increases. The maximum, G*, is the activation energy that must be overcome to
form the nucleus. Once the critical nucleus size, rc, is exceeded, the free energy
decreases monotonically as the nucleus grows to complete the phase transition.
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Fig. 11.3 shows that the nucleation of a new phase is a thermally activated
process, like the diffusional processes we discussed in Chapter 9. In order for the transformation to proceed spontaneously it must first overcome the activation barrier, G*.
To determine the rate at which nuclei of the new phase form under particular conditions,
it is necessary to evaluate the activation energy, G*.
G*
G
rc
Fig. 11.3: The free energy to form a nucleus as a function of its effective
radius, r.
11.3.2 The activation energy for homogeneous nucleation
The free energy change on forming the nucleus is the sum of two terms. First, a
volume, V of the phase is created from the parent . The associated change in the free
energy can be written
G = VGv
11.1
where Gv is the free energy change per unit volume of the nucleus. Since Gv relates to
the free energy change of the whole system, rather than that of the nucleus alone, there is
some subtlety in its evaluation. We discuss this matter in more detail below. However,
when and are incompressible phases of a one-component system, Gv is just the free
energy change per unit volume for the transformation at the given temperature.
Secondly, an interface appears between the nucleus and the phase. The interface
adds the free energy
G = S
11.2
where > 0 is the interfacial tension of the interface and S is its area. It follows
that the free energy change on forming a spherical nucleus of radius, r, is
4
G = 3 r3Gv + 4r2
11.3
The critical nucleus size and the activation energy for homogeneous nucleation
can be found by differentiating equation 11.3. The maximum is reached when
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d(G)
= 4r2Gv + 8r = 0
dr
11.4
Hence the critical radius is

2
rc = - G
11.5
and the activation energy for homogeneous nucleation is the value of G when r = rc.
We use the symbol GH to designate the activation energy to create a spherical,
homogeneous nucleus:
GH = G(rc) =
163
3(Gv)2
11.6
11.3.3 The nucleation rate

The rate of homogeneous nucleation is proportional to the frequency with which
free energy fluctuations of magnitude G* occur in the system. Hence
GH
n fi Nexp- kT
11.7
where n is the number of critical nuclei that form per unit area per unit time and N is the
number of atom sites per unit volume, any one of which can be the locus of the center of
the critical nucleus.
However, there is a second kinetic term that influences the nucleation rate. To
create a critical nucleus it is necessary to assemble the material that it contains. Even in a
one-component system the growth of the nucleus requires transport of material across the
interface from to . When and are solid solutions the composition of the nucleus
ordinarily differs from that of the parent phase, so species must diffuse to the nucleus in
order for it to grow. When and are condensed phases these are diffusional processes
that require thermal activation. Let QD be the relevant activation energy. Then the net
nucleation rate for a transformation between condensed phases is given by an equation of
the form
(GH+QD)
n = ANexp
kT
11.8
where A is a pre-exponential factor.

Equation 11.8 reveals two important qualitative features of the kinetics of
nucleated transformations in condensed phases.
The first is that a nucleated
transformation never happens precisely at the transformation temperature; the system
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always overshoots the transformation temperature at least slightly to provide the positive
driving force that is needed to trigger the transformation. Let T0 be the transformation
temperature. When T = T0, Gv = 0 and GH is infinite. The nucleation rate, n, is zero
when T = T0. A nucleated transformation can only occur when the temperature passes T0
to create a finite driving force, Gv.
ln(n)
T
nucleation limited
growth limited
Fig. 11.4: The variation of the nucleation rate with temperature.

The second important kinetic feature applies only to transformations that occur in
condensed systems on cooling. In these systems the nucleation rate has a maximum at a
finite temperature below T0, and the transformation can be suppressed by quenching the
system at a sufficiently rapid rate. To see this note that near T0 the nucleation rate is
dominated by the activation energy for nucleation, GH, since GH >> QD. We refer to
this regime as nucleation-dominated. In the nucleation-dominated regime the nucleation
rate is given approximately by
GH
n ~ ANexp- kT
11.9
Since the magnitude of Gv ordinarily increases rapidly at temperatures slightly below

T0, GH decreases rapidly and n increases exponentially..
However, the increase in Gv eventually has the consequence that GH falls
below QD. When this happened the nucleation rate is given approximately by
QD
n ~ ANexp- kT
11.10
We refer this regime as growth-dominated since the kinetics of growth limit the
nucleation rate. Since QD is approximately constant with temperature, the nucleation rate
decreases exponentially as the temperature decreases in the growth-dominated regime.
The balance of these two effects causes the nucleation rate to vary with
temperature as shown in Fig. 11.4. It increases at high temperature, decreases at low
temperature, and has a maximum at an intermediate temperature that roughly corresponds
to the change from nucleation to growth control.
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11.3.4 The initiation time

The consequence of the maximum in the nucleation rate is perhaps more clear
when we plot the time required to initiate the transformation as a function of temperature
below T0. Defining the initiation time () for the transformation as the time required to
form at least one nucleus per unit volume then
= (n)-1
11.11
and varies with the temperature as shown in Fig. 11.5.

ln()
nucleation limited
growth limited
Fig. 11.5: The initiation time () as a function of temperature for a nucleated transformation that occurs on cooling.
ln()
Fig. 11.6: Contrast between the c-curve behavior of a transformation that

happens on cooling and the monotonically decreasing initiation
time of a transformation that happens on heating.
Fig. 11.5 shows the characteristic c-curve behavior of a nucleated transformation
in a condensed phases on cooling. The initiation time decreases rapidly when the
material is cooled below the transformation temperature, T0, but then reaches a minimum
(the nose of the transformation curve) and increases exponentially if the system is cooled
further. The transformation initiates at approximately the temperature at which the
cooling curve intersects the c-curve. Hence the undercooling that precedes the start of
the transformation increases with the rate of cooling. The transformation can be suppressed entirely by cooling the system so rapidly that it passes the nose of the initiation
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curve, provided that initiation at low temperature takes an arbitrarily long time. It is also
often possible to control the temperature at which a nucleated transformation proceeds by
quenching to suppress the transformation and then re-heating to the desired reaction
temperature. As we shall discuss below, this freedom facilitates control of the
microstructure of the product phase.
Note that the kinetic features that are illustrated in Figs. 11.4-5 apply only to
transformations that happen on cooling. Consider the reverse transformation, , that
happens when the temperature is increased to above T0. Both nucleation and growth become easier the further the temperature rises above T0, so the initiation time decreases
monotonically. The kinetic behavior of nucleated transformations of the type and
are contrasted in Fig. 11.6.
11.4 HETEROGENEOUS TRANSFORMATIONS

Homogeneous nucleation is relatively easy to describe, but is often difficult to
achieve in practice. The reason is that there are usually catalytic sites where nuclei can
form with relative ease. The common heterogeneous nucleation sites include free
surfaces, grain boundaries, pre-existing precipitates, inclusions and dislocation tangles.
Each of these sites includes a defect whose excess energy is at least partly recovered
when the nucleus forms, lowering the total energy of the nucleation event.
11.4.1 Nucleation at a grain boundary
As an example, consider the formation of a nucleus on a grain boundary, as illustrated in Fig. 11.7. If the spherical nucleus is simply placed on the boundary it eliminates
a small area of boundary. Since the boundary has a positive tension, , the energy
S is recovered in nucleation, which decreases the free energy required to form the
nucleus.
(a)
(b)
Fig. 11.7: (a) A nucleus formed at a grain boundary showing the elimination of a section of the boundary. (b) The nucleus deforms into
a lens shape to destroy more boundary area.
A more complete analysis shows that a nucleus that would be spherical in the bulk
takes a lens shape on the boundary, as shown in Fig. 11.7b. This is the shape that
minimizes the total free energy change
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G = GvV + S + S
11.12
The nucleation barrier is set by the maximum of G, which is

*
Gb = GHf(/)
11.13
where f(/) is a catalytic factor that is less than 1 and decreases as the ratio
/ increases.
The rate of nucleation on the grain boundary is given by an equation of the form
11.8 with the difference that G* is the activation energy for grain boundary nucleation
and the pre-factor is proportional to the number of grain boundary sites per unit volume
(Nb):
*
Gb + QD
n b = ANbexp
kT
11.14
*
When the undercooling is small, the transformation is nucleation-limited. Since Gb <

GH the rate of grain boundary nucleation is usually much greater than the rate of
homogeneous nucleation . However, at large values of the undercooling the transformation is growth-limited, and homogeneous nucleation dominates since Nv >> Nb.
11.4.2 Other heterogeneous nucleation sites
ln()
T
grain boundaries
volume heterogeneities
homogeneous sites
Fig. 11.8: Diagram showing a possible sequence of dominant nucleation

sites in a polygranular solid that contains heterogeneous nucleation sites.
Nuclei also form at other heterogeneous sites such as free surfaces, junction lines
and nodes in the polygranular network of grain boundaries, and internal heterogeneous
sites such as precipitates, inclusions or dislocation tangles. The nucleation rate at the pth
heterogeneous site is given by an equation of the form
*
Gp + QD
n p = ANpexp
kT
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where Gp is the activation energy for nucleation on a site of type p and Np is the
*
number density of such sites. The value of Gp depends on the nature of the site, and is
generally less than the activation energy for homogeneous nucleation. However, Np <<
Nv, so nucleation at heterogeneous sites is most important when the undercooling is small
and the transformation is nucleation-limited.
In a typical nucleated transformation there are several active nucleation sites.
The nucleation rate is the sum of the rates of all of them. Grain boundary nucleation
tends to dominate in transformations of polygranular materials at small values of the
undercooling. Heterogeneous sites that are distributed through the volume, such as preexisting precipitates and dislocation tangles, become important at larger values of the
undercooling, and homogeneous nucleation dominates when the undercooling is very
large. This situation is illustrated in Fig. 11.8.
When there are several different sets of heterogeneous nucleation sites it is often
possible to control the product microstructure by selecting the dominant one. For
example, by cooling a polygranular solid slowly through the transformation temperature,
the transformation may be made to initiate at a low value of the undercooling where grain
boundary nucleation is dominant. The microstructure of the transformed product will
then be set by crystallites that nucleated and grew from grain boundaries. If the solid is
quenched past the nose of the initiation curve and then re-heated to a temperature well
below the nose of the curve the transformation may be made to nucleate homogeneously
through the volume.
ln()
T
grain boundary precipitates

precipitates in grain interiors
...
Fig. 11.9: Alternative heat treatments for a precipitation-hardening alloy.
Slow cooling leads to precipitation on grain boundaries.
Quenching followed by re-heating causes precipitation through
the volume.
The possibility of controlling the nucleation site is critical to the processing of
many materials. An important particular example is the precipitation hardening of
structural alloys. The mechanical strengths of many structural alloys are enhanced and
controlled by introducing a dense distribution of fine precipitates through the volume. If
these precipitates appear at the grain boundaries instead, they not only fail to strengthen
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the alloy, but embrittle the alloy by introducing preferential paths for intergranular
fracture. The precipitates are forced into the grain interiors by quenching the alloy to
suppress nucleation on the grain boundaries, and then re-heating to induce precipitation at
a low temperature where nucleation happens predominantly in the interiors of the grains.
The alternative heat treatments are diagrammed in Fig. 11.9.
11.5 THE THERMODYNAMICS OF NUCLEATION

Assuming that the parent phase in which a nucleus forms has a given temperature,
pressure, and chemical content then its equilibrium is governed by the Gibbs free energy.
The change in Gibbs free energy on forming a homogeneous nucleus of volume, V, and
surface area, S, is
G = GvV + S
11.16
where Gv is the free energy change per unit volume of the nucleus, the thermodynamic
driving force for the transformation.
However, equation 11.16 is not as straightforward as it might appear. Gv is the
free energy change of the whole system ( + nucleus) when the nucleus forms. If we are
to understand the driving force for nucleation it is necessary to evaluate Gv in terms of
the state of the nucleus itself. Both the pressure and the composition of the material
within the nucleus will, generally, differ from those within the bulk phase. The
conditions of mechanical equilibrium for material enclosed in a spherical surface with
radius, r, and tension, , require that its pressure satisfy the equation
P - P =
2
r
11.17
The pressure difference is very large when r is small. Moreover, when and are solutions then the composition of the nucleus is a variable, and will adjust itself to
minimize its thermodynamic potential. To understand these, and related phenomena that
influence the nature of the material that actually nucleates in a phase transition we must
consider the thermodynamics of nucleation.
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11.5.1 The thermodynamic driving force for nucleation

To find the thermodynamic potential that governs the behavior of the nucleus
itself we use the construction shown in Fig. 11.10. Let the volume within which the
nucleus forms be separated from the remainder of the phase by an imaginary boundary,
as shown in the figure. Since the nucleus is very small compared to the phase, the
temperature, pressure and chemical potentials in the phase are not perceptibly changed
by the formation of the nucleus. The ambient phase acts as a thermodynamic reservoir
that fixes T, P and the chemical potentials {} within the small subvolume that contains
the nucleus.
The region within the imaginary boundary shown in Fig. 11.10 is an open system.
As shown in Chapter 7 (Sec. 7.4.3) the thermodynamic potential that governs its equilibrium is the work function
= E - PV - kNk
11.18
which must have a minimum value when the open system is at equilibrium. The change
in on the formation of the nucleus is the sum of volume and surface terms:
= vV + S
11.19
where v is the change in work function per unit volume of the nucleus. Since
- PV
v = V = - P
11.20
It follows that the change in the work function per unit volume of the nucleus is just the
negative of the change in pressure:
v = - (P - P)
11.21
...
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Fig. 11.10: A small nucleus forms within the outlined volume in a

parent phase of homogeneous , which acts as a
thermodynamic reservoir.
Comparing equations 11.21 and 11.16 shows that the thermodynamic driving
force for nucleation, the change in the Gibbs free energy of the system (+) as a whole,
is equal to the change in the value of the work function of the nucleus alone:
Gv = v = - (P - P)
11.22
Hence the activation barrier that opposes homogeneous nucleation is (eq. 11.6)
GH =
163
3(P)2
11.23
and the critical radius is

2
rc = P
11.24
Comparison with equation 11.17 shows that the critical nucleus satisfies the condition of
mechanical equilibrium for the pressure drop across the interface.
To calculate the activation energy to form a critical nucleus it is necessary to have
an estimate for the pressure difference, P = (P - P), between the two phases at the
ambient values of T and {}. Since thermodynamic measurements are usually made in
vacuum or at atmospheric pressure the function, P(T,{}), that gives the pressure of a
phase as a function of its temperature and chemical potentials is rarely known. The
quantity that is known or easily measured is the change in the Gibbs free energy on
transformation at constant temperature and pressure,
g = g(T,P,{x}) - g(T,P,{x})
11.25
where g is the molar density of the Gibbs free energy. When the molar volume of the
product phase, v, is independent of pressure and composition it is possible to relate P
to this quantity. The relation is simplest for a one-component system.
11.5.2 Nucleation in a one-component system
When a phase nucleates from the condition of chemical equilibrium requires
that the chemical potential be the same in both phases. Since the nucleus has pressure,
P, while the phase has pressure, P, we must have
(P) = (P)
11.26
The Gibbs free energy of a one-component system is

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G = E - TS + PV = N
11.27
where is the chemical potential. Hence the molar free energy is

G
g=N =
11.28
The free energy change per mole for a transformation in which a homogeneous phase is
replaced by at the ambient pressure, P, can hence be written
g(P) = (P) = (P) - (P)
= (P) - (P)
11.29
where (P ) is the chemical potential in the nucleus of the that forms in at P, and
we have used eq. 11.26 to obtain the second form of the right-hand side. The change in
chemical potential with pressure at constant temperature is just the molar volume, v:
=V =v
PT
N
...
11.30
Gv = -P
=> metastable
equilibrium
=>
Gv
T0
Fig. 11.11: Illustration of the driving force for nucleation at temperature,

T, when the product phase, , is an incompressible phase in a
one-component system.
Hence equation 11.29 can be re-written
g(P)

v dP
=-
P dP = = - v(P - P)
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where v is the molar volume of the phase, and we have assumed that the phase is incompressible, as most condensed phases are to a good approximation. It follows that
- P
g(P)
= Gv
v
11.32
where Gv is the change in free energy per unit volume when phase is replaced by
at pressure P, as illustrated in Fig. 11.11.
11.5.3 Nucleation from a supersaturated solid solution
An important structural transformation in a multicomponent solid is precipitation
from a supersaturated solid solution, which happens, for example, when the system is
cooled from a one-phase into a two-phase field. A prototypic example is illustrated in
Fig. 11.12. A binary system that is initially in the one-phase field is cooled into the
two-phase + field to initiate precipitation of . If the supersaturated solution is
metastable the precipitation reaction is a nucleated structural transformation.
If the volume of the phase is nearly independent of its pressure and composition
the free energy change on forming a nucleus of it in the body of can again be written
G = vV + S
~ Gv
V + S
11.33
Where the driving force, Gv , is the free energy change per unit volume for the
formation of from at ambient temperature and pressure. However, the free energy
change, Gv , depends on the precise composition of the phase in the nucleus.

L
+L
+L
Fig. 11.12: A binary system with a eutectic phase diagram. When an

solution is cooled along the dashed line it becomes supersaturated with respect to precipitation of .
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To find Gv
we begin by recalling that the free energy of a binary solution is
G = E - TS + PV
= ANA + BNB
11.34
where the symbols A and B label the two components. To calculate the free energy
change for precipitation of from at constant T and P, let the precipitate take in NA
atoms of component A and NB atoms of component B. The free energy change is
G = G + G

= NAA - A + NBB - B
11.35
If the total number of atoms in is N then NB = xN, NA = (1-x)N, and G = Ng,

where g is the free energy per atom in the phase and x is the mole fraction of B in the
phase. Equation 11.35 can then be re-written

G = Ng - xB - A - A
= N{g - [g - (x-x)]}
11.36
where is the relative chemical potential, = B - A, and x is the solute concentration

in the phase. It follows that
Gv
= n{g - [g + (x-x)]}
11.37
where n is the number of atoms per unit volume of .
- g
x e
x
x
xe
x B
Fig. 11.13: Free energy curves of and phases. A supersaturated solution of composition x is metastable with respect to
precipitation of at any composition in the shaded region.
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The phase is metastable with respect to the formation of a precipitate of that
has any composition for which Gv is negative. The range of composition for which
Gv < 0 has a simple graphical representation, which is shown in Fig. 11.13. Since
g
= x
1.38
the value of the relative chemical potential, , in the metastable solution is the slope
of the line that is tangent to the free energy curve g(x) at concentration x. Hence the
term in brackets on the right-hand side of equation 11.37 is the equation of the tangent
line. The value of the term in braces in equation 11.37 at a given value of x [g(x)] is
the negative of the difference between the value of g on the tangent line at x and the
value of g(x) on the free energy curve, as shown in the figure. The supersaturated
solution is metastable with respect to the formation of a nucleus with any composition,
x, at which the tangent line to g at x lies above the free energy curve.
There is, however, a preferred composition for the nucleus; the composition that
maximizes Gv minimizes G*, the activation energy for nucleation.

The
composition that maximizes Gv can be found from the condition
d(Gv )
dx
= 0 = n[ - ]
11.39
Hence the composition, x, that maximizes the driving force for nucleation is the
composition at which the relative chemical potential, , in the phase is equal to the
potential, , in the parent phase. Graphically, it is the composition, x, where the
tangent line to the free energy curve of the phase, g, parallels the tangent line to g at
x. This composition is indicated in Fig. 11.13; note that it is greater than the
equilibrium composition, xe , of the phase at the precipitation temperature.

The kinetic equations that govern a nucleated transformation in a binary system
are formally the same as in the case of the one-component system, though now the
activation energy, QD, is the activation energy for interdiffusion of the B-component.
The c-curve that governs the initiation of a precipitation reaction has the same qualitative
form and interpretation as that which governs a structural transformation in a onecomponent system, and heterogeneous nucleation has the same qualitative effects on the
kinetics and the morphology of the precipitation reaction.
11.6 NUCLEATION OF NON-EQUILIBRIUM STATES

The phase that nucleates from a metastable parent phase need not be in the state
that is in equilibrium at the given temperature and pressure. The nucleated phase may be
a non-equilibrium state of the preferred product phase, or it may be a different phase of
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the system entirely. Examples of both phenomena can be inferred from the results of the
previous section. First, the initial composition of a nucleus that forms in a binary
solution is different from its equilibrium composition, as shown in Fig. 11.13. Second,
the pressure within the nucleus is ordinarily much higher than that in the parent phase, as
indicated by equations 11.23 and 11.26. If the most stable phase of the system depends
on the pressure then the phase that nucleates from the metastable parent may be a high
pressure phase rather than the phase that is in equilibrium under the ambient conditions.
Kinetic factors also affect the state of the product phase. Generalizing equation
11.15, the rate of formation of nuclei whose state is designated by the index, i, is
*
Gi + Qi
n i = ANiexpkT
11.40
where G*i is the activation energy to form a critical nucleus in state (i), Qi is the
activation energy for growth of the nucleus, and Ni is the density of sites at which the
nucleus can form. The actual state of the nucleus is the one that maximizes the
nucleation rate. We already saw an example of this in heterogeneous nucleation; when a
heterogeneous site decreases G* by an amount that is great enough to provide a large
value of n, the nuclei appear predominantly at heterogeneous sites. By the same
reasoning, if the structure or composition of the nucleus can be changed so that n is
increased, the nuclei tend to have that structure or composition.
This general principle is responsible for many important (and, sometimes,
unanticipated) phenomena that influence nucleated phase transformations. We will
specifically consider three in this section: congruent nucleation, in which the phase that
initially forms in a solid solution has the same composition as the parent, coherent
nucleation, in which the phase that nucleates shares the crystal lattice of the parent, and
Ostwald nucleation, in which the phase that nucleates is a high-temperature, metastable
phase.
11.6.1 Congruent nucleation
It is relatively difficult to form a nucleus that has a chemical composition very
different from that of the parent phase because the excess solute must be gathered by
diffusion. It is, therefore, often easy to suppress precipitation from a multicomponent
parent phase by cooling it rapidly. However, when the undercooling is sufficiently large
an alternative transformation path is available; the parent phase loses equilibrium with respect to the nucleation of the product phase at the same composition. A transformation
from a multicomponent parent phase to a product phase with the same composition is
called a congruent transformation. The nucleation of a congruent phase is called
congruent nucleation. Since congruent nucleation requires no long-range diffusion it is
often kinetically preferred to incongruent nucleation when both are possible.
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The thermodynamic relations that lead to congruent nucleation are illustrated in

Fig. 11.14, which shows the free energy curves for hypothetical and phases at a given
temperature. Let the system be in the phase, and let its composition (x) be increased
slowly. The phase is preferred until the system enters the two-phase (+) region at
the composition xe . For compositions between x e and x0 the system is out of

equilibrium, but, since the -phase is thermodynamically stable (its free energy curve is
concave) and its free energy is below that of the phase at the same composition, it can
only approach equilibrium by nucleating a B-rich phase. This situation continues until
the composition passes the value x0 at which the and free energy curves intersect.
For compositions above x0, however, the free energy curve is lower and the phase
can nucleate congruently.
= +
xe
x0
= +
xe
Fig. 11.14: Free energy curves for a binary system at given temperature
showing composition ranges for incongruent and congruent
nucleation.
A system that undergoes a congruent transformation may be left in a homogeneous, metastable state, as in the transformation in Fig. 11.14, or the
transformation may continue to equilibrium through subsequent decomposition, as in the
path + shown in the figure.
T2< T1
T1
Fig. 11.15: Free energy curves of and L phases at temperatures above

(T1) and below (T2) the congruent transformation
temperature.
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One of the most common examples of congruent nucleation is in the rapid

solidification of liquid solutions. When a liquid solution first enters a two-phase region
on cooling, its free energy curve is related to that of the solid phase (call it ) as shown in
the lower part of Fig. 11.15: the composition of the liquid solution is to the right of the
intersection of the and L free energy curves, and solidification can only occur through
nucleation of A-rich phase. However, as the temperature is lowered the increasing
relative stability of the solid has the consequence that the intersection of the and L
free energy curves is displaced to higher concentrations. Eventually the liquid becomes
metastable with respect to a congruent transformation to , as illustrated by the upper
free energy curves in Fig. 11.15.
L
T
+L
+
L
A
Fig. 11.16: A possible locus for the L congruent transformation line

in a binary phase diagram.
The locus of the congruent L transition can be plotted on the phase diagram,
and has a form like that shown in Fig. 11.16. For all compositions and temperatures to
the left of the L line shown in the figure the free energy of the liquid solution is
greater than that of an solid solution of the same composition, and a direct L
transformation can occur through congruent nucleation of the phase. In the system
illustrated in this figure a L congruent transformation can occur even at temperatures
within the two-phase (+) region if the liquid solution is cooled rapidly enough to
suppress nucleation of the eutectic constituent. Because there is no need for long-range
diffusion the activation energy for growth of a congruent nucleus, QD, is the activation
energy for a direct jump across the interface, which is more like the activation energy for
grain boundary diffusion than the much higher activation energy for bulk diffusion.
Hence the nucleation of congruent particles is ordinarily predominant at temperatures
where a congruent nucleus can form.
A possible form for the kinetic transformation diagram of a system that can form
congruent nuclei is shown in Fig. 11.17. The congruent transformation is not possible
until the temperature is well below the equilibrium transformation temperature, but is
then nucleated at a much more rapid rate.
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Congruent solidification is particularly desirable in the processing of alloys of

materials that have very high melting points or very low diffusivities, since it is difficult
to remove chemical heterogeneities that may develop during the equilibrium
solidification of these materials. To achieve it, materials scientists have developed the
technique of rapid solidification, in which the liquid is quenched very rapidly to suppress
nucleation of the solid phase until the undercooling is high enough for congruent nuclei
to form. It is usually only possible to achieve such high rates of cooling when the liquid
has a very high surface-to-volume ratio so that heat can be extracted quickly. The
conventional techniques of rapid solidification include pouring the liquid onto a chilled
substrate that is rapidly moving, so that the liquid solidifies rapidly into a thin ribbon, or
spraying the liquid in the form of small droplets into a chilled gas, so the droplets solidify
rapidly into a fine powder.
ln()
incongruent
nucleation
congruent
nucleation
Fig. 11.17: A possible kinetic diagram for the transformation of a multicomponent system that can transform congruently.
Another important application of rapid solidification is the formation of metallic
glasses. As discussed in Chapter 5, to force a metallic material into a glassy structure it is
necessary to cool it rapidly enough to suppress nucleation of the crystalline phase so that
the lower, glass transition temperature, Tg, can be reached. Given the high rate of
congruent nucleation it is very difficult to suppress nucleation by this mechanism. Hence
the systems that are used to form metallic glasses tend to be solutions whose
compositions are chosen so that the congruent nucleation temperature is very low.
L
+L
+L
glasses
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Fig. 11.18: Illustration of the formation of glasses in a eutectic system.

The congruent nucleation lines are shown. Glasses form in
the low-temperature bay between where congruent nucleation
is not possible.
A simple example is shown in Fig. 11.18. In order to form a glass in a system
with a simple eutectic phase diagram it must be possible to cool the system to a
temperature well below the crystallization temperature without inducing congruent
nucleation. If the congruent nucleation lines for the two terminal solid solutions
extrapolate to a temperature below Tg without crossing, as they do in the example shown,
glasses can be formed by quenching into the low-temperature "bay" between the
congruent nucleation lines. This is generally only possible when the two species have
very low solubilities in one another. Otherwise the congruent nucleation lines intersect
above Tg. Hence metallic glasses tend to be concentrated solutions of species that have
low solubility, such as solutions between metals and metalloids like B, P or C.
11.6.2 Coherent nuclei
When the parent phase is a solid the work to form the nucleus is also affected by
its coherency, or crystallographic registry with the parent lattice. A phase that can
nucleate coherently has a very low interfacial tension, , because its atom planes are in
registry with those of the surrounding matrix, but has a significant strain energy
distributed through its volume since it is necessarily distorted to maintain registry with
the matrix. The coherent nucleus can only form when the undercooling is sufficiently
high that
Gv
+ eel < 0
11.41
where eel is the (positive) elastic strain energy per unit volume and Gv is the
(negative) free energy change for transformation to the phase in its relaxed (unstrained)
state. Assuming spherical shape, the work to form the coherent nucleus is, then,
GH =
16c3
3(Gv + eel)2
11.42
where c is the interfacial tension of the coherent nucleus. Since c is usually much less
than , the interfacial tension of an incoherent nucleus, the work to form the coherent nucleus is less than that to form an incoherent nucleus when the undercooling is
appreciable.
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ln()
incoherent
nucleation
coherent
nucleation
Fig. 11.19: Example transformation kinetics for a solid-solid transformation in which the product phase can form coherently.
The kinetics of a solid-solid transformation that can be nucleated coherently are
illustrated in Fig. 11.19, and are qualitatively similar to those in Fig. 11.17. If the
transformation occurs at small undercooling the nucleus must be incoherent, since only
the unstrained state of the product phase is stable. However, the large interfacial tension
of the incoherent phase usually has the consequence that it is difficult to nucleate, and
then only forms at heterogeneous sites such as grain boundaries. Coherent nucleation is
not possible until the undercooling is appreciable, but is then kinetically preferred. In
fact, most solid-solid transformations that occur in the bulk are initiated by coherent
nuclei.
The coherency of the product phase is ordinarily lost when the nucleus grows to
significant size. The reason is that the strain energy due to the coherent strain increases
with the volume of the nucleus, while the surface energy increases with the surface area.
There is always a volume large enough that it is energetically favorable for the growing
particle to replace its coherent interface with an incoherent one that relaxes the
transformation strain. The larger the strain energy, that is, the larger the crystallographic
mismatch between the parent and product phases, the smaller the size at which the
incoherent interface is preferred. The mechanism by which coherency is lost is usually
the accumulation of dislocations at the interface to destroy the registry between the two
phases.
Coherency strains may also affect the shape of the nucleus. It often happens that
the strain energy of a coherent particle is minimized when the particle takes the shape of
a thin plate that lies on a particular crystallographic plane of the matrix (called the habit
plane). The tendency to assume a plate-like shape is, however, opposed by the surface
energy since a platelet has a much higher surface area per unit volume than a more
equiaxed figure. For this reason solid nuclei are found in a variety of shapes. Those that
have very high coherency strains tend to nucleate as platelets with specific habit planes.
Those that fit better in the parent matrix tend to nucleate as spheres, but even then the
shape tends to evolve into a cubic and, eventually, a platelet morphology as the particle
grows. Since many of the important properties of solid precipitates, such as their
resistance to cutting by dislocations, are affected by their shapes, the prediction and
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control of precipitate shape is an important engineering consideration in designing and

processing structural materials.
11.6.3 Nucleation of metastable phases: the Ostwald rule
When the parent phase in a phase transformation is far away from equilibrium it is
often the case that several product phases are possible. For example, when a condensed
phase is deposited from the vapor on a chilled substrate the nucleated phase can be a
liquid or a solid, and can often have any one of several solid structures. The phase that
actually forms will be the one whose nucleation rate is the highest. In the context of
classical nucleation theory this is the phase that minimizes the total activation energy,
G* + Q.
Neglecting differences in the activation energy for growth, the preferred phase
minimizes the nucleation barrier, G*. In the case of homogeneous nucleation,
GH =
163
3(Gv + eel)2
11.43
where we have included the elastic strain energy, eel, to allow for coherency. This expression suggest two factors that may promote the formation of a metastable phase.
The first factor is the interfacial tension. Phases that have low surface tension are
strongly preferred. Since phases that have high entropy tend to have low interfacial tensions, there is a strong tendency for high temperature phases to nucleate preferentially at
temperatures well below their equilibrium temperature range. The initial deposits on
solid surfaces are often liquid at temperatures well below the melting point. The solid
phases that form during vapor deposition on a cold substrate are often high temperature
or amorphous structures (glassy phases have particularly low interfacial tensions).
The second factor is the strain energy, eel. This factor is important when the
product phase is coherent, as it often is when a solid nucleates in the bulk or when a solid
is deposited onto a crystalline substrate. If there is a metastable phase that provides a
better lattice match than the equilibrium phase, it is often preferred. There are many
examples of precipitation reactions in the solid state that lead to metastable precipitate
phases that are preferred because of their relatively small strain with the solid matrix.
The hardening precipitates in most important aluminum alloys are examples. The various
carbide precipitates in steel are even more common examples; the equilibrium precipitate
in carbon steel is graphite, which has a very poor match with the iron lattice. The
structures of deposited films are also often determined by lattice compatibility with the
substrate.
A particular product phase can also be formed catalytically by ensuring that there
are heterogeneous nucleation sites that prefer that phase to any other. For example, if it is
desirable to deposit a crystalline thin film whose surface is a particular crystallographic
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plane, this can often be done by depositing it on a substrate that provides a particularly
good crystallographic match to that plane (the substrate is said to be epitaxial to the
desired film). The good interfacial match lowers both and eel for a film with the
desired orientation, and, hence, promotes its nucleation.
These considerations suggest that the nucleation of metastable phases should be a
common phenomenon. It is. The prevalence of metastable products was so well documented by the early years of the present century that W. Ostwald was led to formulate it
as a law of science. His Ostwald Rule states essentially that if a metastable phase can
form in preference to the equilibrium one, it will. The Ostwald Rule is something of an
overstatement, but it contains more than a grain of truth.
11.6.4 Sequential Nucleation in a Eutectic
Some phase transformations involve two or more products that nucleate sequentially. A simple and important example is the solidification of a binary system that has a
eutectic phase diagram. Three qualitatively different cases occur. They are illustrated by
the three compositions shown in Fig. 11.20
First consider solidification at the composition x1. Assuming that the solid
reaches equilibrium, it transforms in two discrete steps. First, the solid solution, ,
nucleates out of the liquid, and grows until it consumes the liquid. The result will
ordinarily be a polygranular solid solution. At equilibrium, the solution is
homogeneous in composition. However, on further cooling the solution enters the twophase (+) field, and becomes metastable with respect to precipitation of the phase.
The final, two-phase state is obtained through a sequence of two independent reactions
that involve independent nucleation events: nucleates and grows at the expense of the
liquid, and then, at a lower temperature, nucleates and grows out of . The kinetics of
these sequential reactions can be analyzed separately.
x1
x2
x3
L
+L
+L
...
Fig. 11.20: Eutectic phase diagram showing solidification at three compositions.
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A qualitatively different behavior occurs if the liquid phase has the eutectic
composition, x3. In this case the liquid first becomes metastable with respect to a twophase mixture of and . In order to form the eutectic constituent, both must nucleate.
...
Fig. 11.21: Schematic illustration of the nucleation of the eutectic constituent in a eutectic microstructure.
A mechanism for the nucleation of the eutectic constituent is illustrated in Fig.
11.21. Let one of the two solid phases, say , nucleate first. Since the nucleus is lean
in solute (B), it rejects solute, so that a solute-rich "halo" forms around it, as shown in the
Fig. 11.21a. The nucleation of the B-rich -phase is relatively easy in this solute-rich
halo, so a nucleus of forms on . As the nucleus grows it rejects solvent (A), and
develops an A-rich halo on the side away from the growing nucleus. A second nucleus forms in this A-rich halo, creating a B-rich region to the far side of it. The
sequential nucleation eventually leads to a composite nucleus of the eutectic constituent:
a laminate of the and phases like that shown in Fig. 11.21d. The eutectic nucleus
shown in Fig. 11.21d can grow vertically into the liquid by the process described in
Chapter 9; and lamellae grow side-by-side at essentially constant composition as
solute is redistributed over the short distance between the head of the lamella and the
heads of the lamellae that border it. The eutectic nucleus extends itself sideways by
alternate nucleation of the and phases, creating the colonies that appear in the
eutectic microstructure described in Chapter 9.
While the nucleation of a eutectic constituent is a bit more complicated than the
nucleation of a single product phase, it is thermally activated and is described by kinetic
equations that have the same form as those for the simpler transformation. Hence
the initiation time for a eutectic transformation has a typical c-curve dependence on the
undercooling.
The solidification of a liquid solution that has an intermediate composition, such
as the composition x2 in Fig. 11.20, involves two sequential reactions. When this
solution is cooled into the two-phase (+L) region, at T, it becomes metastable with
respect to the nucleation of solid solution. However, the nucleation of cannot
complete the reaction. Even if the liquid solidifies to the extent needed for equilibrium,
there is residual liquid when the eutectic temperature, TE, is reached. Hence the eutectic
constituent must also nucleate to complete the transformation.
The nucleation of the eutectic is facilitated in this case, however, because islands
of -phase are already present. The eutectic reaction simply continues the growth of the
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particles that are already present by nucleating -phase heterogeneously on the preexisting (proeutectic) . Hence the nucleation of the eutectic constituent is relatively
easy.
ln()
T
T
TE
...
Fig. 11.22: Initiation kinetics for nucleation on cooling a liquid of composition x2 in Fig. 11.21. Proeutectic nucleates below T.
The eutectic constituent (+) nucleates below TE.
The initiation times of the sequential nucleation reactions behave as shown in Fig.
11.22. When the temperature falls below T the liquid is metastable with respect to the
nucleation and growth of proeutectic . The nucleation of obeys the usual kinetics of
L transformations. When the system falls below TE it is metastable with respect to
the nucleation and growth of the eutectic constituent. The eutectic constituent nucleates
heterogeneously on the proeutectic , and is, hence, relatively easy to form. However,
some undercooling is still required to initiate the heterogeneous nucleation of and form
the eutectic.
1000
T (C)
800
+ carbide
+
+ carbide
600
0.5
1.0
1.5
weight percent carbon
2.0
...
Fig. 11.23: A portion of the Fe-C phase diagram. If a sample of the
composition shown by the dashed line is cooled, it first
precipitates , then the eutectoid constituent, + Fe3C.
The behavior of a system that undergoes a eutectoid reaction (solid solution transforms to a mixture of two solid phases, +) is entirely similar; the only difference
is that the high-temperature phase is a solid solution rather than a liquid. For example,
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the Fe-C phase diagram appears as shown in Fig. 11.23. If a sample of -phase with the
composition shown by the dashed line is cooled to low temperature, the initiation kinetics
for the proeutectoid, reaction and the eutectoid reaction, + Fe3C, combine
as shown in Fig. 11.22.
11.7 RECRYSTALLIZATION
In the nucleated reactions we have discussed to this point the product phase of the
transformation is a different phase from the parent. However, there is one important case
in which the parent and the product are examples of the same phase: the recrystallization
reaction that occurs when a deformed metal is heated to a sufficiently high temperature.
Recrystallization is a common phenomenon, and is the reaction that is ordinarily used to
control the grain size of a structural alloy.
The thermodynamic driving force for recrystallization is the free energy of nonequilibrium defects in the deformed material. As we shall discuss when we come to mechanical properties, the plastic deformation of a material introduces a high density of
dislocations and other defects. These defects have energy, and hence add to the free
energy of the material. While there are mechanisms, called recovery processes, that
gradually eliminate them, the rate of recovery of non-equilibrium defects is very slow at
ordinary temperatures. The alternative mechanism is recrystallization: the nucleation and
growth of new, relatively defect-free grains.
The actual mechanism of nucleation of a defect-free grain in a deformed material
can be subtle. The dislocation network in a deformed material is inhomogeneous and
evolves with time at high temperature, and there are always small volumes of essentially
defect-free material that may act as pre-existing embryos of defect-free phase. However,
we can obtain a qualitative understanding of recrystallization by assuming that the
nucleation of recrystallized grains is mechanistically the same as the nucleation of grains
of a new phase. Since the material is solid and relatively incompressible, the driving
force for nucleation is approximately, Gv , the free energy per unit volume of the
defects in the deformed phase. The surface tension is , the interfacial tension of a
grain boundary in the material. The activation energy for homogeneous nucleation of
defect-free grains is, hence,
GH =
16()3
11.44
3(Gv )2
Heterogeneous nucleation of recrystallized grains is both possible and likely,

since the deformed solid is polygranular and also has a dense distribution of internal
clusters of defects that may act as heterogeneous nucleation sites. Hence the activation
barrier, G*, that opposes the nucleation of a recrystallized grain should be less than
GH by some factor:
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*
Gn = fpGH
(f < 1)
11.45
where fp is the catalytic factor of the dominant heterogeneous sites, which are denoted by
the index, p. The elementary growth step for a nucleus of recrystallized grain is the
migration of an atom across a grain boundary. The nucleation rate for recrystallization
process should, hence, obey a rate equation of the familiar form
*
Gp + QD
n = ANpexp
kT
11.46
where Np is the number of heterogeneous sites per unit volume.

While the rate equation that governs the nucleation of recrystallized grains in this
model, eq. 11.46, is formally the same as that which governs the other transformation
processes we have studied, it is qualitatively different in two respects. First, the
*
activation barrier that opposes the nucleation of recrystallized grains, Gn , decreases
with the degree of prior deformation, but is nearly independent of the temperature, since
the free energy of a dislocation changes very little with temperature. The second important difference is that recrystallization is induced by heating rather than cooling, and,
hence, cannot be suppressed.
From equation 11.46, the initiation time for recrystallization can be written in the
simple form
QR
ln() = - ln(n) = - ln(ANp) + kT
11.47
where QR, the activation energy for recrystallization, is

*
QR = Gp + QD
11.48
It is relatively insensitive to the temperature, but decreases with the degree of prior deformation. If the logarithm of the initiation time is plotted as a function of 1/kT, as in Fig.
11.24, the result is a straight line of slope QR. If the initiation rate is plotted for various
degrees of prior deformation, the result is a series of straight lines whose slope decreases
with prior deformation.
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decreasing prior
deformation
ln()
Q
R
1/kT
...
Fig. 11.24: The initiation time for recrystallization as a function of temperature and degree of prior deformation.
The time to initiate a recrystallization reaction in a typical material is
prohibitively long unless the temperature is a significant fraction of the melting point (T
greater than about 0.4 Tm), and unless the prior deformation is substantial. The
temperature at which recrystallization initiates in a given, reasonably short time is the
recrystallization temperature. The recrystallization temperature decreases with the extent
of prior deformation.
11.8 GROWTH
11.8.1 Primary growth and coarsening
After nucleation, grains of the product phase grow to complete the transformation
and establish the final microstructure. This happens in two distinct stages. First, the
product phase grows at the expense of the parent. In this stage, primary growth, the product phase grows relatively quickly until it consumes the parent or, in the case of a
precipitation reaction, reaches a volume fraction close to its equilibrium value. At the
end of primary growth, however, the product is usually in a fine-grained microstructure
that may also be chemically inhomogeneous. In the second stage, secondary growth, or
coarsening, the grains or particles of product phase grow at the expense of one another to
reconfigure themselves into a more stable microstructure.
Two things must happen for the product phase to grow. The material that is to be
incorporated into the growing particle must be delivered to the interface, and it must
cross the interface to enter the product phase. Either step may govern the kinetics of
growth. We therefore distinguish two types of growth on the basis of the slower, or ratelimiting step: diffusion-controlled growth and interface-controlled growth.
The diffusional processes that may control growth are the diffusion of mass and
heat to or from the growing interface. A first-order phase transformation generates latent
heat. If the heat of the reaction is not transported away from the interface it accumulates
there and raises the temperature (if it is positive) until the reaction stops. Unless the
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transformation is congruent, chemical species must also diffuse to (or from) the growing
interface to produce the composition of the product phase. Since mass diffuses more
slowly than heat, mass diffusion is usually the rate-limiting step for primary growth in
multicomponent systems.
The material that diffuses to the surface of the growing phase must also be
incorporated into it. When the growing phase is congruent and the interface is rough and
irregular on the atomic scale this step requires no more than a diffusional jump across the
interface. The jump across the interface is, nonetheless, often the rate-controlling step for
congruent transformations in solids where the latent heat of the transformation is small
and the thermal conductivity is high. Even when the growing particle has a composition
very different from that of the matrix, the interface still controls the rate of growth if its
nature is such that the addition of atoms is difficult.
The mechanisms of growth control the grain morphology of the product phase,
and may also control the chemical distributions within them. Chemical heterogeneities
are particularly common in as-solidified materials. In the usual case, solidification
initiates when the liquid is cooled into a two-phase (solid + liquid) region, and proceeds
through the growth of a solid whose composition is initially very different from that of
the liquid. Solute is rejected into the liquid and accumulates there. Since the rate of
solidification is much more rapid that the rate of diffusion in the solid state, the
composition of the solid cannot adjust itself during solidification, so the final product is a
chemically heterogeneous solid in which the last material to solidify is very rich in solute.
In the following sections we discuss the features of growth in more detail. We
shall first consider primary growth, and first examine the case of interface control,
because it is the simplest. We then discuss diffusion-controlled primary growth,
chemical segregation during primary growth, and secondary growth (coarsening).
11.8.2 Time-temperature-transformation (TTT) curves
The net rate of a phase transformation reflects the kinetics of growth as well as
the kinetics of nucleation. It is customary to represent the overall rate graphically by
plotting the time required to achieve various fractions of transformation as a logarithmic
function of the temperature. A hypothetical example is given in Fig. 11.25, which shows
lines for 1%, 50% and 99% transformation as a function of the undercooling. When such
a diagram refers to transformation under isothermal conditions, which can ordinarily be
achieved by quenching the sample and then re-heating it to the appropriate temperature, it
is called a TTT-diagram (time-temperature-transformation). In practice the first curve on
a TTT diagram is drawn at some small fraction, since the very first transformation is
difficult to detect. For the same reason the last curve is drawn at a fraction near, but less
than 100% transformation.
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ln(t)
T
99%
50%
1%
...
Fig. 11.25: A TTT-curve for a hypothetical nucleated transformation that
occurs on cooling.
The extent of transformation in a sample that is cooled continuously through the
phase transformation is also of interest. A diagram like that in Fig. 11.25 that plots the
time to achieve a given fractional reaction on continuous cooling is called a CCT diagram
(continuous cooling transformation). The two kinds of diagrams have a qualitatively
similar appearance, but differ in detail since the incremental progress of a nucleated
transformation as it is cooled through a temperature, T, depends on events that happened
at higher temperature as well as on those that transpire at T.
11.9 INTERFACE-CONTROLLED GROWTH

11.9.1 Isotropic growth of a congruent phase
The simplest example of interface-controlled growth is the growth of a solid
phase that has the same composition as the matrix, has an incoherent interface, and
produces a latent heat of transformation that is small enough that it is conducted away to
preserve an essentially constant temperature. While this combination of conditions may
seem stringent, it pertains, at least roughly, to a large number of solid-solid and liquidsolid transformations, including many structural transformations in one-component
solids, recrystallization reactions, massive (congruent) transformations in solid solutions,
and eutectic solidification.
In the simplest case the temperature and composition are constant and the ratelimiting step for growth is the motion of an atom across the interface from the ambient to
the growing phase, as illustrated in Fig. 11.26. If the interface is incoherent and the surface of the growing phase is rough on the atomic scale, then the interface has essentially
the same structure over its whole boundary with the fluid, and the rate of growth is nearly
isotropic (the same in all directions).
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g*
g
...
Fig. 11.26: The free energy change during the motion of an atom across
the interface of a growing particle.
The rate of growth can be understood from the following simple model. Let an
atom cross the interface. Its free energy changes along a line connecting its initial and
final positions roughly as shown in Fig. 11.26. This curve governs atom jumps across the
interface in both directions. To cross the boundary from the ambient to the particle
an atom must overcome the activation barrier, g*; to cross from the particle to the
ambient an atom must overcome the higher barrier, g* + g, where g is the
difference in the free energy per atom between the two phases. If there are n atoms per
unit area of interface, the net flux of atoms across the interface into the particle is
J = J - J
g* + g
g*
= nexp- kT - exp
kT
g
g*
= n exp- kT 1 - exp- kT
11.49
where is the frequency of jumps attempts. Assuming that g is small compared to

kT, we can use the approximation ex 1 - x to evaluate the bracket in eq. 11.49. The
result is
g - g*
J = n kT e kT
11.50
The velocity of the interface (the linear growth rate) is

g - g*
Jv1/3
1/3
= n = nv kT e kT
where v is the atomic volume.
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Equation 11.51 suggests that the congruent growth of a particle is thermally

activated, with an activation energy equal to g*, the activation energy for migration
from to , and a pre-exponential factor that increases with the thermodynamic driving
force for the transformation, g. If the transformation happens on cooling, then g
vanishes at the transformation temperature, T0, and increases with the undercooling.
Since the exponential term decreases monotonically as T decreases, the growth rate
reaches a maximum at some moderate undercooling, and vanishes when the temperature
is very small. If the transformation happens on heating, for example, the recrystallization
reaction, then the rate of growth increases monotonically with the superheating.
The microstructures that result from isotropic growth depend on the type of nucleation that predominates. This is true even if the nuclei are distributed through the
volume. If nuclei form throughout the volume at a roughly constant rate, then the
microstructure at the end of primary growth is obtained by the impingement of grains that
initiated at different times.
The microstructure is an equiaxed, polygranular
microstructure that contains grains with a variety of sizes, with curved grain boundaries.
Such a microstructure is found, for example, in recrystallized iron. In a second common
case nuclei form throughout the volume, but at discrete, heterogeneous sites that are
exhausted very early in the transformation. In this case the microstructure contains
equiaxed grains with almost straight grain boundaries. Such a microstructure is
sometimes seen in recrystallized FCC metals, such as high-Ni stainless steels. If the
nuclei form heterogeneously on a surface then the microstructure contains parallel,
columnar grains that grow out from the surface. Such a microstructure is often found in
solid films, in metal ingots that were cast by pouring into a chilled mold, and in
weldments in metals.
11.9.2 Interface control at stable surfaces
A second class of growth processes that are interface-controlled includes the
growth of crystals whose surfaces are relatively immobile because of the difficulty of
adding atoms onto them. The processes that behave in this way generally have two
characteristics: the growing crystal has a highly anisotropic surface tension, and the
connection between the crystal and its ambient is such that the crystal can develop a form
in which it is bounded by low-energy planes. The reactions that satisfy these constraints
include the growth of compounds or crystals with complex structures from the liquid or
vapor, the precipitation of crystalline compounds from aqueous solution, and, at least in
some cases, the growth of coherent precipitates in solids.
The structural reasons for interface control

The reason that these reactions are interface-controlled is the structure of the
growing surface. As we discussed in Chapter 4, when a solid has an anisotropic surface
tension its surfaces tend to be made up of segments of low-energy surface (ledges) that
are terminated by steps. Such surfaces grow by the addition of atoms at the steps, as
illustrated in Fig. 11.27a. This mechanism causes the ledges to grow relatively rapidly
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over the surface, as shown in Fig. 11.27b, until the steps disappear at the boundary and a
low-energy surface is presented to the ambient.
(111)
(hkl)
...
Fig. 11.27: The structure of a stepped surface, and its growth to achieve
a low-energy interface.
If the growing crystal has a highly anisotropic surface tension, the growth of a
low-energy surface is relatively difficult. The low-energy surface moves in the direction
normal to itself through the lateral growth of ledges, as shown in the figure. Its growth
terminates when all of the existing ledges have exhausted themselves at the boundary,
and can only continue if new ledges form. However, in the absence of a catalytic
mechanism, the formation of a new ledge requires the nucleation of a disc of material on
the plane crystal surface. The nucleation of a disc of new plane is opposed by the line
tension of the step on the periphery of the disc, and is, hence, a thermally activated
nucleation process that is difficult to accomplish unless the thermodynamic driving force
is high.
Hence materials with strongly anisotropic surface tension tend to develop
polygonal shapes that are bounded by low-energy surface planes. When they have
achieved these shapes they grow at the rate at which new ledges can nucleate on the lowenergy surfaces. Unless the undercooling is high, the normal growth rate is slow.
This phenomenon is responsible for the fact that oxide minerals and other
materials of complex crystal structure often appear "crystalline" in their natural form,
while normal metals and elemental semiconductors do not. Materials with complex
crystal structures tend to have anisotropic surface tension, since the atom density in the
surface plane depends strongly on the indices of the plane. The anisotropy is particularly
strong in compounds with partly ionic bonding, a class that includes most oxide minerals,
since only certain crystal planes are electrically neutral (contain equal numbers of
positive and negative charges). Hence many minerals grow from solution as polygonal
bodies whose macroscopic shapes reflect their atomic structure, and their growth is
interface-controlled unless the driving force for the transformation is very high. On the
other hand, metals tend to have close-packed or nearly close-packed structures whose
interfacial tensions are not strongly dependent on orientation. They normally form in
irregular shapes that do not reflect their inherent crystallinity. (We are so accustomed to
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associate crystallinity with macroscopic form that most undergraduates are as surprised
as I was to learn that metals are crystalline at all.)
However, there are at least two cases in which metallic phases exhibit a
crystalline appearance and an interface-controlled growth. One is when the metal has a
complex crystal structure. An example is antimony (Sb), which has a rhombohedral
structure in which pairs of Sb atoms are closely bound to one another. An Sb-rich phase
can be crystallized out of a Pb-Sb solution (as it is in one of the E45 labs) by choosing a
composition on the Sb-rich side of the eutectic. The solidified Sb crystals are nearly
cubes. A second example is found in the shapes of coherent precipitates in solids. These
often appear as discs or plates with flat interfaces whose habit plane parallels the plane
that provides the best match between the crystal structures of the precipitate and the
matrix. Moreover, these coherent interfaces are relatively immobile during growth. The
platelet shapes of these precipitates reflect two factors, minimization of the interfacial
tension between the precipitate and matrix and simultaneous minimization of the elastic
energy due to coherency, that ordinarily promote the same shape and growth behavior.
The screw-dislocation mechanism of growth

In order for a faceted crystal to grow under small supersaturation there must be a
mechanism that continually produces mobile ledges on its low-energy surfaces. Several
such mechanisms have been proposed; all of them involve dislocations that penetrate the
free surface. The simplest and best documented is the screw-dislocation mechanism that
is diagrammed in Fig. 11.28.
...
Fig. 11.28: The screw-dislocation mechanism of crystal growth. The left
figure shows a growth spiral around an emerging screw dislocation. The right is a side view showing growth steps.
Let a screw dislocation intersect the free surface of a growing crystal, as shown in
Fig. 11.28a. Recalling the discussion of screw dislocations in Chapter 4, the screw dislocation is one whose Burgers' vector, b, parallels the dislocation line. The displacement
introduced by a screw dislocation has the consequence that a given plane of atoms spirals
around the dislocation; since b parallels the dislocation, a Burgers' circuit around the
simplest screw dislocation finishes one atom plane above its starting point. It follows
that a screw dislocation introduces a vertical step when it emerges at a free surface. If
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this step grows laterally across the surface, as drawn in Fig. 11.28a, it develops a spiral
step around the dislocation core that is self-perpetuating; each time the growth of the step
causes the spiral to complete a revolution around the dislocation core, the dislocation
advances one atom plane perpendicular to the interface so that the step is maintained.
The surface near the emerging screw dislocation has the shape shown in cross-section in
Fig. 11.28b. The spiral step is preserved as the growing ledge rotates around the
dislocation, and the interface grows by one atom plane with each revolution.
The screw-dislocation mechanism of crystal growth permits a low-energy surface
to grow normal to itself without successive nucleation events on the plane, and hence
permits the growth of a faceted crystal under a relatively small thermodynamic driving
force. The rate of growth is relatively slow, so almost isothermal conditions are
maintained. An examination of the faceted surface of a growing crystal ordinarily reveals
a number of emerging screw dislocations whose growth spirals overlap to maintain the
growth rate.
Instabilities in interface-controlled growth: whiskers

Under certain conditions of interface control a growing crystal develops an
anomalously high growth rate in one direction leading to the formation of a long, thin
single-crystal "whisker". Whiskers are most commonly observed during deposition from
a vapor or precipitation from a liquid under conditions such that nucleation is confined to
a surface. The surface fixes the base of the whisker, which then grows out from it into
the ambient. Whiskers originated as a scientific curiosity. They are often free of
dislocations, and hence have exceptionally high resistance to plastic deformation. More
recently, whiskers have become important in materials technology, in both the positive
and negative sense. In the positive sense, high-strength whiskers of materials like SiC are
grown commercially and harvested for use as reinforcements in metal-matrix composite
materials (SiC-reinforced aluminum). In the negative sense, whiskers sometimes develop
spontaneously on aluminum conducting lines in microelectronic devices, and cause
electrical shorts by bridging conductors.
Current understanding suggests that several different mechanisms can lead to the
formation of whiskers. All are interface controlled. Two of the best documented are
illustrated in Fig. 11.29.
One mechanism of whisker growth is the screw-dislocation mechanism shown on
the left in Fig. 11.29. Let a small crystallite contain a single screw dislocation that is oriented perpendicular to one face. The face that contains the screw dislocation can grow.
The perpendicular faces cannot grow easily. If the screw dislocation is oriented out of
the plane of the substrate a thin whisker may form and grow by the addition of atoms at
its stepped tip. Whiskers that grow in this way are nearly dislocation-free, and can
actually become dislocation-free if the central screw dislocation eventually glides to the
free surface. This is, therefore, a useful mechanism for creating very strong, almost
perfect whiskers.
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screw
dislocation
surface diffusion
to pinned base
strained solid
Fig. 11.29: Two mechanisms of whisker growth: growth at the tip by a

screw dislocation and growth at the base by surface diffusion
to a pinned droplet on a strained surface.
A second mechanism is shown on the left in Fig. 11.29, and appears to be
pertinent to the growth of whiskers from conducting lines in microelectronic devices. Let
the substrate be strained mechanically, for example, let it be a thin film that is strained by
a lattice mismatch with the body on which it rests. It can be shown that the strained solid
is thermodynamically unstable with respect to the nucleation and growth of an unstrained
mound of material ("hillock") on its surface. However, suppose that this hillock cannot
spread over the surface, most likely because of pinning by surface debris. Then the only
way the nucleated crystal can grow is out of the surface. Since the surface crystal is
unstrained, the free energy is lowered if atoms of the strained substrate migrate to it,
causing a whisker to be pushed out from the bottom as shown in the figure.
11.10 DIFFUSION-CONTROLLED GROWTH

In many important phase transformations the growth of the product phase is controlled by the rate at which the heat of reaction can diffuse away from the interface or the
rate at which the chemical species that preferentially congregate in the new phase can diffuse to it. Common and important examples include the solidification of typical metals
or semiconductors from the melt and the growth of common precipitates in the solid
state. The simplest example is thermal control during congruent solidification from a
liquid, so we shall consider this case first.
11.10.1 Growth controlled by thermal diffusion
Consider the freezing of a solid at constant composition, and assume that the
interface is sufficiently mobile that the solid can grow as rapidly as other conditions
permit. The velocity of the interface is limited by the need to eliminate the latent heat of
solidification.
The temperature at the growing interface

The positive latent heat of solidification has the consequence that, at least shortly
after the transformation begins, the temperature at the growing interface is Tm, the
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melting point of the material. To see this note that if the interface temperature were less
than Tm the solid could grow more rapidly by using its own heat capacity to absorb the
latent heat. Hence the rate of growth increases until T = Tm. But the interfacial
temperature cannot exceed Tm. If it were to do so the solid would melt. The rate of
growth is hence set by the requirement that T = Tm at the growing interface.
To maintain T = Tm the latent heat must be removed from the interface as fast as
it is generated. The primary mechanism is thermal conduction down a temperature
gradient that leads away from the interface. In most cases of solidification, whether the
casting of metal ingots or the growing of semiconductor crystals, the growing solid is
attached to an external wall or fixture that can serve as a heat sink. Hence there is a
negative temperature gradient from the interface into the solid. On the other hand, the
temperature gradient into the liquid may be either positive or negative. It is positive, for
example, when hot, molten metal is poured into a chilled mold to cast and ingot. In this
case the liquid is a source of heat, and the solid can only grow as fast as the sum of the
latent heat of the transformation and the heat that flows in from the liquid can be
conducted away. The temperature gradient into the liquid is negative, for example, when
the liquid is supercooled to below its melting point to induce nucleation. In this case the
latent heat is conducted away by both the solid and the liquid.
Thermal instability: dendrites

Solidification is much more rapid when the liquid is supercooled. However, the
solidification front is also unstable. To see this, consider the example shown in Fig.
11.30, where the liquid temperature is below the melting point.
L
x
...
Fig. 11.30: Initiation of a dendrite during solidification of a supercooled
liquid.
The temperature profile through the interface of a solid that is growing into a
supercooled liquid is illustrated on the left in Fig. 11.30. The maximum temperature is
Tm, at the solid-liquid interface. Now suppose that a small protrusion appears on the
solid surface. It penetrates into the liquid. The liquid that is sampled by the material at
the tip of this protrusion is cooler than that sensed by the trailing surface of the
solidifying solid, so the temperature gradient into the liquid from the tip of the protrusion
is greater than that at the trailing solid surface. Moreover, heat is conducted radially
away from the protrusion into the liquid, while the heat flow from the trailing surface is
one-dimensional. Both factors cause a higher growth rate at the head of the protrusion,
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so the protrusion becomes more and more pronounced. The interface is unstable with
respect to the formation of long, thin dendrites that reach out into the liquid.
As dendrites develop during unstable solidification they extend and branch until
the solidification front comes to resemble a forest of Christmas trees, as illustrated in Fig.
11.31. The dendrites branch for the same reason they formed in the first place. The peripheral surface of a dendrite is an essentially plane surface that thickens by planar
growth. It is unstable with respect to formation of a secondary dendrite, just as the
original interface was. Hence dendrites branch and branch again. (You may be most
familiar with dendrites from the shapes of snowflakes, which are dendritic structures of
ice that form by deposition of ice from cold air supersaturated with water. The old folk
saying that "no two snowflakes are alike" is a semi-accurate description of the statistical
nature of dendrite growth and the almost infinite variety of the branching patterns that
may develop. Is the folklore true? I don't know, and I am not anxious to examine all the
snowflakes that there have ever been to find out.)
...
Fig. 11.31: Dendrites growing into a supercooled liquid.
It is important to recognize that the growth of thermal dendrites, like those discussed above, is peculiar to solidification into a supercooled liquid. If the liquid is above
its melting point then a nascient dendrite that protrudes from the solid surface encounters
temperatures above the melting point of the solid, and remelts. When the temperature of
the liquid is above Tm, a congruent solid can form a stable, planar growth front. This fact
is used, for example, in the growth of large single crystals from the melt. The melt must
be held at a temperature above its melting point and heat extracted through the solidifying
solid; otherwise the solidifying surface is unstable with respect to the formation of
dendrites.
11.10.2 Growth controlled by chemical diffusion
When the product phase has a different composition from the parent and the interface is mobile the rate of growth is limited by the rate of atom transport to the solid
surface. As a simple example, consider the growth of a solid precipitate of phase , of
composition, c, in a matrix of phase, , whose mean composition is c. Assume that the
interface is plane and that growth occurs at essentially constant temperature (as it
ordinarily does when is solid since the latent heat of precipitation in a solid is small).
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c
e
...
Fig. 11.31: Composition profile near the plane surface of a precipitate
growing under diffusion control.
The composition profile across the growing interface is illustrated in Fig. 11.31.
The solute concentration in the precipitate is c. The concentration in the phase well
away from the interface is c. Equilibrium at the interface requires that the solute
concentration in the phase there be ce , the concentration of solute in the phase when
it is in equilibrium with at the interface temperature, T. The concentration gradient in
the phase provides the driving force for the diffusion of solute to the solid surface.
The kinetics of diffusional growth

We can find an approximate relation for the diffusional growth of from the following simple argument. If the solute diffusivity is D, the mean diffusion distance for the
solute in time, t, is, by the arguments of Chapter 10,
x = x2 = 2Dt
11.52
To approximate the width of the precipitate, xp, at time, t, assume that all of the excess
solute (B) atoms that are located within a mean diffusion distance of the center of the precipitate have incorporated into it, leaving behind an layer of solution that has the equilib
rium composition, ce , while the remainder of the solution is unaffected by the growing
interface and has he composition c. The total number of B-atoms in a slab of solution of
width 2Dt and unit cross-sectional area is
NB = nc 2Dt
11.53
where n is the number of atoms per unit volume. The number of B-atoms in a composite
of a precipitate of width, xp, and an equilibrium solution of width, xp - 2Dt is
NB = ncxp + nce [ 2Dt - xp]

Equating the two expressions gives
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xp =
c - ce
c - ce
2Dt
11.55
which suggests that the growth rate, dxp/dt, is given by a relation of the form
dxp
dt = A(c - ce )
D
t
11.56
The linear growth rate increases with the supersaturation of the solid solution, (c - ce
), and decreases with the square root of the time.
While this derivation is based on an oversimplified model, its features are the
same as those obtained by more accurate theoretical analyses of the linear growth rate:
the interface velocity increases with the supersaturation (though not always linearly), and
decreases with the time as D/t .
Constitutional supercooling
It is apparent from Fig. 11.31 that the planar interface of the growing precipitate
treated here is unstable with respect to the formation of dendrites, even when the
temperature is constant. If a small protrusion forms on the surface of the growing
precipitate its tip encounters solution that is richer in solute than the equilibrium value.
Hence the concentration gradient is larger at the tip of the protrusion. Moreover, the
composition gradient at the tip is radial, so the total flux to the protrusion is enhanced still
further over the flux to the plane interface. Consequently, the protrusion extends into a
dendrite, and the planar growth front breaks up into dendritic elements. A transformation
product that differs in composition from its parent phase is even less stable with respect
to dendrite formation than is a congruent product.
Despite this instability, precipitate particles in solids do not ordinarily produce
dendrites until they grow to moderate size. The reason is that there is a minimum lateral
dimension to a growing protrusion, just as there is a minimum size for a stable nucleus.
Small particles are not large enough to generate dendrites; large particles often do.
When the growing crystal is large it is still possible to stabilize its interface by adjusting the temperature gradient to compensate for the concentration-induced instability.
To see how this is done in the particular case of the solidification of a solid solution,
consider the segment of phase diagram shown in Fig. 11.32. Assume that is solidified
out of the liquid at the temperature, T, that is indicated by the dashed line in the phase
L
diagram. The equilibrium concentration of B in the liquid is ce , given by the tie-line
that is drawn in the phase diagram.
Assume that the liquid is heated with respect to the solid so that its temperature
increases with distance from the interface. If the solid were congruent, a positive
temperature gradient would stabilize its surface against the formation of dendrites.
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However, when the solid is incongruent the temperature gradient into the liquid must not
only be positive, it must also be fairly steep.
cL
e(T)
+L
+
c
...
Fig. 11.32: B-rich portion of the eutectic phase diagram of a hypothetical
binary system showing a -L tie lie across the two-phase region and the increased solubility of B in the liquid as the temperature is increased further.
To appreciate this, return to the phase diagram shown in Fig. 11.32. According to
the phase diagram, increasing the temperature raises the solubility of B in the liquid
phase. The solubility is given as a function of T by the equation
L
ce
= ce (T)
11.57
that defines the boundary of the L+ region on the liquid side. Now suppose that the
temperature of the liquid varies as T(x) near the growing solid surface. Substituting this
function into equation 11.57 yields the solubility of B in the liquid phase as a function of
distance from the interface:
L
ce (x) = ce [T(x)]
11.58
The actual composition of the liquid as a function of distance from the interface is
cL(x), and is determined by the diffusion profile. If the temperature rise near the
interface is sufficiently rapid that
L
ce (x) cL(x)
11.59
everywhere, then a protrusion from the solid surface encounters liquid that is unsaturated
with solute, and dissolves. Hence if the temperature and composition profiles are such
that the inequality 11.59 is satisfied, the interface is stable with respect to the formation
of protrusions. On the other hand, if, for x near the interface,
L
ce (x) < cL(x)
11.60
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a protrusion penetrates a supersaturated solution and grows spontaneously, at least for the
distance over which the inequality 11.60 is satisfied. When 11.60 is true the solution is
said to be constitutionally supercooled.
c
c (T1)
c (T2)
c(T3)
c
ce
...
Fig. 11.33: Composition profile near a growing interface with the
solubility profiles associated with three temperature
gradients. The regions of constitutional supercooling for the
gradients T 2 and T 3 are shaded.
The relations that govern the geometric stability of the growing interface are illustrated in Fig. 11.33. Three values of the temperature gradient into the liquid are included:
a steep gradient that stabilizes the interface, and two more shallow gradients that lead to
various degrees of constitutional supercooling.
Equation 11.59 and Fig. 11.33 show that a growing interface is stabilized by a
steep temperature gradient. However, it is difficult to maintain such a gradient more than
temporarily during normal solidification. Since the thermal conductivity of a condensed
phase is much larger than its diffusivity, a steep temperature gradient is quickly
dissipated into a shallow one. For example, we can solidify a solution by pouring it into
a chilled mold, so that heat is extracted through the mold wall. A steep temperature
gradient is established immediately after pouring, and the solidification front from the
wall is initially plane and stable. However, the temperature gradient quickly softens,
generating the succession of conditions indicated by the gradients T 1 to T 3 in Fig.
11.33. After some growth the sample is constitutionally supercooled for a distance ahead
of the growing interface that increases with time. Hence the growing interface becomes
increasingly unstable as it grows. Dendrites almost inevitably appear.
However, dendrite formation can be suppressed in carefully controlled solidification reactions that use special furnaces to maintain a temperature gradient at the interface.
A technologically important example is the growth of large crystals for microelectronic
devices. These must be both structurally and chemically uniform, and hence cannot
tolerate dendrite formation at the interface. In the usual methods for crystal growth from
the melt the growing interface is stabilized by heating the melt in a controlled manner to
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establish a sharp temperature gradient at the interface that is maintained during growth.
Special gradient furnaces have been designed for this purpose.
11.11 CHEMICAL SEGREGATION DURING GROWTH

One of the major practical problems encountered in the processing of
multicomponent systems is the development of undesirable chemical segregations during
diffusional transformations. The clearest example occurs in the solidification of a solid
solution. As a specific example, consider the solidification of the solution indicated by
the dashed line in the phase diagram drawn in Fig. 11.34.
L
+L
+L
...
Fig. 11.34: A eutectic phase diagram showing a composition that would,
ideally, solidify into a homogeneous solid solution.
If the solution indicated by the dashed line were solidified under equilibrium
conditions it would become completely solid at the temperature at which the dashed line
crosses into the single-phase, field. However, a real system that is cast or solidified at
a practical cooling rate is more likely to remain at least partly liquid until the eutectic
temperature, TE, is reached, and solidify into a microstructure that has a chemically
inhomogeneous phase in the interiors of grains or dendrites, while the boundaries of
these are decorated by high-solute material, including some of the eutectic constituent.
To understand why this should happen, assume that solidification starts when the
system is in the two-phase +L region, and assume that solid state diffusion can be ignored, as it usually can be when the phase is a substitutional solution and the system is
cooled at a moderate rate. The first solid to form is rich in A, and causes the liquid to become slightly richer in B. Ideally, when the solution is cooled to lower temperature the
composition of this first solid should adjust to the equilibrium value by incorporating
more of the B-specie. But this chemical redistribution requires diffusion in the solid phase, and cannot happen if solid state diffusion is negligible.
The physical consequence of forming a solid whose composition cannot be
adjusted on the time scale of the solidification process is the same as if the solid were
removed from the system entirely, leaving a solution slightly richer in B. At a slightly
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lower temperature the liquid solution deposits an A-rich solid, though it is slightly less
rich in A than the material that solidified previously, and becomes richer still in B. A
continuation of this process causes the composition of the residual liquid to follow the
liquidus curve (the boundary between the liquid and the two-phase region) all the way
down to the eutectic point, as shown in Fig. 11.35. The last bit of liquid to solidify has
the eutectic composition. It is trapped between the grains or dendrites of since these
are formed by the material that solidifies earlier in the reaction.
L
T
+L
...
Fig. 11.35: Schematic drawing of a section of the eutectic phase diagram
illustrating the evolution of the composition of the solid and
liquid when an A-rich solution is solidified rapidly. The last
material to solidify has the eutectic composition.
The chemical segregation that develops during solidification is disadvantageous
for at least three reasons. First, it degrades the properties of the solidified material,
particularly its mechanical properties. In most systems the eutectic constituent has poor
mechanical properties; it is either very soft or very brittle. In the structure discussed
above this weak material is located in the worst possible place, in a semi-continuous
network along the grain boundaries. This morphology maximizes any deleterious effect
on the mechanical properties. Second, segregation interferes with further processing.
For example, in structural materials the solid solution in a system that has a phase
diagram like that shown in Fig. 11.34 is precipitation hardened by introducing a fine
dispersion of precipitates into the interiors of the grains. It is not possible to achieve
a homogeneous precipitation of the phase if the parent is chemically heterogeneous;
the precipitation times and temperatures vary from point to point with the composition.
Third, the presence of the eutectic constituent makes it difficult to homogenize the
material to remove segregation. Homogenization, which was discussed in Chapter 10,
requires solid state diffusion, and hence proceeds more rapidly the higher the temperature
at which it is carried out. But an alloy with the inhomogeneous microstructure described
here must be homogenized at a temperature below the eutectic temperature, TE. The
eutectic constituent melts at TE, and the alloy will fall apart if heated to a higher
temperature. This problem has the consequence that alloys that have components with
high melting points and eutectics with low melting points often cannot be homogenized
at all, and require elaborate treatments, such as rapid solidification processing, before
their potential can be realized.
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In many engineering applications it is desirable or necessary to use

multicomponent systems in the as-solidified condition. The metal alloys used for
welding and joining usually must be used in the as-solidified condition. There is often a
large financial benefit to making parts of complex shape by direct casting. Special
casting or welding alloys have been created for these purposes. Their compositions are
carefully engineered to avoid the most serious problems encountered in the nonequilibrium solidification of more conventional alloys.
11.12 GRAIN GROWTH AND COARSENING

When a phase transformation has gone essentially to completion the material is
usually left in an unstable microstructure that evolves further. The as-solidified material
contains residual chemical heterogeneities of the type discussed in the previous section,
has a polygranular microstructure, and often contains small second-phase precipitates. If
the material is maintained at high temperature the chemical heterogeneities tend to
homogenize. At the same time the grains grow and the precipitates coarsen. The
principal driving force for grain growth and precipitate coarsening is the surface energy.
These processes lower the total surface area, and hence the total surface energy.
Both grain growth and coarsening are thermally activated diffusional processes.
In order for a grain to grow material must diffuse across its boundary from a neighboring
grain. On balance, large grains grow at the expense of small ones. Since the large grain
has less surface area per unit volume, the free energy per atom (chemical potential) decreases with grain size. There is, hence, a thermodynamic driving force for diffusion
across the boundary from the small grain to the larger one. Large grains grow, small ones
disappear.
The mechanism of precipitate coarsening is slightly different. Large precipitates
grow at the expense of smaller ones by diffusion through the matrix. Let the precipitates
be spherical particles in a binary solution at constant temperature and let the precipitate
phase have a composition that is richer in solute that the matrix. The larger the
precipitate particle, the smaller its free energy per atom, and, hence, the smaller its
relative chemical potential. Since = B - A = g/x increases with x for both the
matrix and the precipitate, the solute concentration that is in equilibrium with the
precipitate decreases as the precipitate grows. Hence the matrix is relatively depleted in
solute near the large precipitates, and relatively enriched near the smaller ones. The
concentration gradient from the small precipitates to the large ones induces solute
diffusion to the large precipitates, which causes the matrix composition to exceed the
local equilibrium value, so the large precipitate grows. The smaller precipitate shrinks as
matrix diffusion removes solute, which is restored by the dissolution of the precipitate.
The rate of grain growth or coarsening increases with the temperature in a predictable way, with the result that either process can be controlled, and used to fix the
mean grain size or mean precipitate size of a material to a reasonable degree of accuracy.
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11.13 INSTABILITIES
At the beginning of this chapter we discussed the fact that there are two basic
phase transformation mechanisms: nucleated transformations and instabilities. When the
parent phase is stable the transformation must be nucleated. The probability of
nucleation depends on the thermodynamics of both the parent and product phases. When
the parent phase becomes unstable it must transform. As diagrammed in Fig. 11.1,
instabilities define the limits of metastability of the parent phase, and depend on its
properties alone.
Solid phases are distinguished from one another by differences in one or more of
three characteristics: composition, chemical or electromagnetic order, and basic crystal
structure. If we identify the basic crystal structure with the distribution of atom sites,
without regard to the specific types of atoms that occupy them, and define the state of
order (segregation of atom types onto specific sets of lattice positions) so that perfect
order corresponds to the most complete possible segregation for the given composition,
then these three characteristics are independent. For a solid phase to be thermodynamically stable it must be stable with respect to small changes in any one of the three
characteristics: a change in the state of order at fixed composition and structure, a change
in the structure at fixed composition and state of order, and a decomposition into regions
of different composition on a fixed, ordered lattice. When a solid phase becomes
unstable then, barring fortuitous degeneracy, the initial instability concerns only one of
these three characteristics. While other characteristics may change as the transformation
proceeds, the instability that triggers the transformation inevitably involves the composition, the structure, or the state of order alone. There are common phase transformations
that are initiated by instability with respect to each of the three characteristics of
structure.
First, and most familiar, because of its importance in the heat treatment of steel,
are the transitions in which the crystal structure changes spontaneously at constant
composition. For historical reasons, these are called martensitic transformations.
Second, there are instabilities in which a random solid solution becomes unstable
with respect to decomposition into two solutions with the same structure, but different
compositions, and spontaneously develops a fine scale chemical heterogeneity. There is
always an instability of this type when a miscibility gap appears in the phase diagram.
The transformation that is induced by a compositional instability is called a spinodal decomposition. (The name derives from the characteristic shape of the surface that results
when the relative chemical potential of a system that undergoes a spinodal composition is
plotted as a function of temperature and pressure, which we shall not illustrate here.)
Third, it is both possible and fairly common for disordered solid solutions to order
spontaneously when the ordering reaction is first-order and the system is cooled to well
below the equilibrium ordering temperature. These reactions are called ordering instabilities. Such instabilities affect disordered solutions in systems that have ordered
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phases. An ordered phase may also become unstable, and be replaced by another that is
very like it.
Another group of instabilities includes the mutations that were discussed in
Chapter 9 and in Section 11.2. These are simpler in the sense that the equilibrium
transformation temperature and the stability limit of the parent phase are the same; the
parent phase simply becomes the product at the phase transformation. The glass
transition is a mutation, as are almost all of the electromagnetic transformations in solids,
and some chemical ordering reactions.
We have already described the common mutations. In the following sections we
discuss the martensitic, spinodal and ordering transitions.
11.14 MARTENSITIC TRANSFORMATIONS

The martensitic transformation takes its name from the spontaneous structural
change that occurs when carbon steel is rapidly quenched from an elevated temperature at
which the (FCC) phase is stable. The microstructural features of the transformation
were studied at an early date by a German scientist named Martens, so the product is
called "martensite". The martensitic transformation is central to the processing of a
number of important structural steels and has, consequently, received a great deal of
attention. However, similar transformations occur in many other metal alloys and oxide
ceramics. Transformations that have martensitic characteristics have even been observed
in biological systems.
Fig. 11.36: The body-centered tetragonal cell within an FCC structure

that transforms to BCC when given the tetragonal distortion
shown at right.
The simplest model of the martensitic transformation (which is oversimplified,
but sufficient for our purposes) begins from the observation that the driving force for a
structural transformation, Gv, increases monotonically as the temperature is lowered
below the equilibrium transformation temperature. If the material is cooled so rapidly
that nucleation is suppressed then the driving force may become large enough to force a
structural transformation through a spontaneous mechanical distortion of the crystal
lattice.
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To see how this might happen in the specific case of the FCCBCC
transformation in iron, consider two adjacent cells of the FCC structure, as shown in Fig.
11.36. It is possible to define a body-centered tetragonal cell within the FCC crystal
structure, as shown in the figure. This cell has height, a, while its other edges have length
a/ 2 . It can be transformed to BCC by giving it the net tetragonal distortion shown in
the figure to make its edge lengths equal. This distortion preserves the atomic volume if
the length and width are expanded slightly as the height is compressed.
At finite temperature the atoms in a solid undergo thermal vibrations about their
equilibrium positions. When the basic structure is stable the free energy increases as an
atom moves away from its equilibrium position, so the amplitude of the vibration is small
and centered about the equilibrium site. However, some of the vibrational modes of the
atoms in the FCC structure carry them in the direction of the tetragonal distortion that
would generate BCC. If the driving force for the FCCBCC transformation is great
enough it can enhance the amplitude of the vibrational modes that carry the system
toward BCC. There are regions within the FCC crystal in which the atoms are already
distorted toward BCC, for example, near properly oriented grain boundaries or clusters of
dislocations. When the thermodynamic driving force becomes sufficiently large, small
volumes of FCC material in these regions spontaneously distort into the BCC structure,
initiating a mechanical lattice transformation from FCC to BCC. When these small
volumes are large enough to grow into the FCC matrix their boundaries propagate as a
mechanical disturbances at the speed of sound, transforming the structure as they move.
In fact, one can often hear a martensitic transformation in steel.
ln()
T
Ms
Mf
nucleated transformation
martensitic
transformation
Fig. 11.37: Plot of the transformation initiation time () against T for a

system that can transform by a martensitic mechanism.
Since a pure martensitic transformation is caused by a thermodynamic instability,
it cannot be suppressed; when the driving force is great enough the transformation
happens spontaneously. Such transformations are called athermal. If an athermal
martensitic transformation occurs in a given system, it only happens if the system is
quenched rapidly enough to suppress transformation by nucleation and growth, and then
initiates at a particular value of the undercooling, at a temperature called the martensite
start temperature, Ms. The martensite start temperature is represented by a horizontal line
on the transformation initiation plot shown in Fig. 11.37. If the system is cooled slowly,
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as illustrated by the upper arrow in the figure, the transformation is nucleated. If the
system is quenched rapidly, as indicated by the lower arrow, the transformation is
martensitic.
The martensite transformation starts at the temperature, Ms, but in most cases it
does not go to completion at that temperature. To sustain the transformation the temperature must be lowered further. The martensite fraction is a function of the temperature,
and approaches completion at the temperature, Mf, the martensite finish temperature.
The reason for this behavior is the strain induced in the structure by the martensite
transformation. When the structure is locally changed as, for example, in an FCC
BCC transformation like that shown in Fig. 11.36, the new phase does not fit properly in
the crystalline matrix of the parent phase, and hence distorts the region of parent phase
around it. For this reason the individual particles of the martensite tend to appear in the
form of thin plates, or laths, that are internally defective, and have a very small volume
fraction at the martensite start temperature, Ms. To sustain the transformation the
thermodynamic driving force must be sufficient to form additional product phase in a
matrix that is strained by the prior transformation; hence the undercooling, T, must be
increased continuously as the transformation proceeds. The progress of a martensitic
transformation through the successive formation of product phase is illustrated in Fig.
11.38.
(a)
(b)
Fig. 11.38: Successive stages in the martensite transformation on

cooling: (a) near Ms; (b) on further cooling below Ms.
The pattern of an athermal martensite transformation often looks like that shown
in Fig. 11.38. The new phase first appears as thin plates that cross grains and terminate at
grain boundaries. The subsequent transformation produces smaller plates that tend to
subdivide the untransformed regions until the transformation is complete.
Because the martensite transformation involves a distortion of the lattice it is promoted if the solid is subjected to mechanical stresses (forces) that act to deform the solid
in the direction of the crystallographic transformation. Hence Ms increases when a
suitable stress is applied, and the enhanced martensite is called stress-induced martensite.
If the solid is plastically strained at a temperature below T0, high local internal stresses
are caused by interaction of the dislocations that cause plastic deformation. These
stresses can be very effective in promoting the martensite transformation. The
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temperature at which martensite forms on deforming the material is called Md, and can be
a hundred degrees or more above Ms in steels. This deformation-induced martensite has
important effects on the mechanical properties of many austenitic (FCC) stainless steels,
which have kinetically stabilized FCC structures and are used at temperatures above Ms,
but below Md.
ln()
Ms
Mf
martensitic
transformation
Fig. 11.39: Two cooling paths that lead to a mixed microstructure in

which the transformation is accomplished partly by
nucleation and partly by the martensitic mechanism.
It is also possible to produce mixed microstructures in which the product phase is
achieved partly through a martensitic transformation and partly through a nucleated transformation. Two methods for doing this are diagrammed in Fig. 11.39. In the first the
sample is cooled slowly to initiate the transformation by a nucleated mechanism, but then
quenched before the nucleated transformation is complete. The residual material
transforms by a martensitic mechanism. In the second the material is quenched below Ms
to accomplish a partial transformation to martensite, but is then held isothermally (or
heated slightly) so that the residual material transforms by the nucleated mechanism.
Finally, since the martensite transformation is caused by a structural instability it
does not permit chemical redistribution. If the transformation is one that would normally
create a two-phase microstructure, as, for example, the transformation of carbon steel on
cooling which creates a mixture of the BCC -phase and a carbide precipitate phase
(Fe3C), the martensitic transformation creates a single-phase microstructure that is supersaturated with solute. In the particular case of carbon steel the martensitic product is
supersaturated with carbon, and is usually distorted into a body-centered tetragonal
(BCT) structure by the ordering of excess carbon interstitials in asymmetric octahedral
interstitial sites, as discussed in Chapter 4. The resulting structure is mechanically very
hard, but tends to be brittle (easily fractured). Hence martensitic carbon steels are often
heated to a moderate temperature and held for some time to permit precipitation of the
excess carbon in Fe3C precipitates. This process is called tempering, and leads to a
product that is still very hard, but is much more difficult to fracture (that is, it is tougher).
If the martensitic transformation of carbon steel happens at relatively high
temperature (that is, when Ms is a relatively high temperature) or if the steel is cooled
relatively slowly between Ms and Mf then carbides may precipitate out of the
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supersaturated martensite while the transformation is going on. The carbides form from
carbon that is rejected from the supersaturated martensite as it grows. This autotempered
martensite is a mixture of martensitic plates and carbide precipitates. It is called Bainite
after the American metallurgist, E.C. Bain, who was among the first to study it. The
microstructure of Bainite depends on the kinetic balance between the growth of
martensite and the rate of carbide precipitation, and many complex microstructures are
possible.
11.15 SPINODAL DECOMPOSITION

Spinodal decomposition describes a phase transformation in which a solid
solution spontaneously decomposes into a mixture of two solutions that have the same
crystal structure and degree of order. Spinodal instabilities appear near miscibility gaps
in the phase diagram, where a parent solid solution decomposes into two solutions of
different composition.
11.15.1 Spinodal instability within a miscibility gap
L
T
'
A
'+"
x
''
B
...
Fig. 11.40: The phase diagram of a binary system that contains a
miscibility gap in a homogeneous solid solution.
An example of a miscibility gap is shown in Fig. 11.40. This figure shows the
phase diagram of a binary system that forms a solid solution () at all compositions at
high temperature, but divides into two solid solutions, ' and ", at lower temperature.
The thermodynamic reasons for the appearance of a miscibility gap were
discussed in Chapters 8 and 9. A miscibility gap appears when the when the free energy
of the solution has the behavior shown in Fig. 11.41. At T > Tc, where Tc is the
temperature at the top of the miscibility gap, the free energy depends on composition as
shown in the left-hand figure in 11.41; g is a concave function of x, so the equilibrium
phase is a homogeneous solution at all compositions shown. At T <Tc, on the other hand,
the function, g(x), has double minima as shown in the right-hand figure in Fig. 11.41.
The two concave branches of the curve represent different phases, with the same crystal
structure, that share a common tangent. When the composition falls within the region of
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the common tangent the solution divides into a mixture of two solutions with different
compositions, which generates the two-phase region in the equilibrium phase diagram.
T > Tc
T < Tc
'
"
g
'
"
'+"
...
Fig. 11.41: Free energy curves for a solid solution in a system that exhibits a miscibility gap (a) above and (b) below the temperature, Tc, at the top of the gap.
It is often possible to preserve a homogeneous solution in a metastable state
within a miscibility gap by cooling it quickly enough to suppress nucleation. However,
the range of metastability is limited. The parent solution becomes unstable with respect
to spontaneous, spinodal decomposition once it reaches a temperature such that its
composition is significantly inside the miscibility gap. The thermodynamic source of the
instability is illustrated in Fig, 11.42. The solution is unstable when the free energy
becomes a convex function of x, that is, when 2g/x2 0.
x1 x2
g
'
''
...
Fig. 11.42: The free energy curve of a solution that has a miscibility gap.
The solution is stable when g(x) is concave, for example, at
x1, but unstable when g(x) is convex, as at x2.
To see this consider the free energy curve shown in Fig. 11.42, which is drawn at
a temperature for which the solution has a miscibility gap. As we discussed in Chapter 9,
if the system is a mixture of two distinct states, its free energy is given by the intersection
of a straight line connecting these two states with a vertical line at the overall
composition of the system, x. This graphical relation is illustrated in Fig. 11.42 for two
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compositions, x1, where g(x) is concave, and x2, where it is convex. A homogeneous
solution of composition x1 is at least metastable. Because g(x) is concave, decomposition
into two solutions with compositions very close to x1 leads to an increase in the free
energy. The solution is, hence, stable with respect to spontaneous fluctuations in its local
composition.
On the other hand, a homogeneous solution of composition x2 is unstable. If it is
separated into two solutions with slightly different compositions, the free energy
decreases. In a real solution atoms continually move by diffusional jumps, so that the
composition of any small volume within the solution fluctuates constantly. When the
overall composition is such that 2g/x2 0, these local fluctuations decrease the free
energy, and grow spontaneously to decompose the solution.
The stability limit for the homogeneous solution is the locus of points for which
2g/x2 = 0, that is, the locus of inflection points in the free energy curve, g(x), as the
temperature is lowered. These points generate spinodal lines that can be plotted in the
phase diagram, as in the example given in Fig. 11.43. The spinodal lines define a
spinodal gap in the phase diagram within which a homogeneous solution is unstable.
x1
T
T1
x2
''
'
T2
spinodal
gap
Fig. 11.43: A solid solution containing a miscibility gap, with the curves
that define the stability limits of the solid solution drawn inside.
11.15.2 Spinodal decomposition
To illustrate how a homogeneous solution behaves when it is cooled into a miscibility gap, we consider the two compositions, x1 and x2, that are labeled in Fig. 11.43.
Symmetric spinodal reactions

The composition, x2, is the composition at the top of the miscibility gap. A solution of this composition is unstable as soon as it is cooled below Tc. As a consequence it
inevitably decomposes by a spinodal mechanism. Solutions with composition near x2
develop the symmetric spinodal that is illustrated in Fig. 11.44.
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Spinodal decomposition develops in a characteristic pattern like that illustrated in

Fig. 11.44. Spontaneous diffusion of the solute causes the development of alternate regions that are rich and poor in solute. However, the interfaces between these regions cannot be arbitrarily sharp without introducing a high interfacial tension that would oppose
the transformation. As a consequence the composition varies in a roughly sinusoidal
pattern like that shown in Fig. 11.44, in which the composition varies gradually with
distance.. An analysis of the kinetics of spinodal decomposition shows that there is a
particular wavelength of the spinodal wave that can grow more rapidly than any other
under a given set of conditions. Hence solutions that decompose by the spinodal
mechanism tend to have sinusoidal composition profiles with a particular dominant
wavelength.
Fig. 11.44: Development of a symmetric spinodal wave in a solution

with x x2 in Fig. 11.45.
Note that during spinodal decomposition the solute diffuses uphill, from regions
that are poor in solute to regions that are rich. This behavior violates Fick's First Law,
but should not be surprising. As we discussed in Chapter 10, the actual thermodynamic
driving force for diffusion is the chemical potential gradient rather than the composition
gradient. When an unstable solution undergoes spinodal decomposition the chemical
potential gradient is in the opposite direction to the composition gradient; the free energy
is reduced as the solution divides into regions that are alternately rich and poor in solute.
Rather different microstructures may result from spinodal decomposition, depending on the number of dimensions in which the spinodal waves develop. In some
materials the spinodal wave is essentially a one-dimensional wave; the formation of a
wave in one dimension suppresses the development of similar waves in the perpendicular
directions. In this case the final microstructure contains alternate lamellae of ' and ".
In other materials waves develop simultaneously in two or three perpendicular directions.
Two-dimensional decomposition leads to a microstructure in which one phase (that with
the lower volume fraction) appears in rod-shaped grains in the matrix of the other. In
three-dimensional decomposition the minority phase ultimately forms equiaxed grains in
the matrix of the other.
Asymmetric spinodal reactions
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The transformation behavior of the solution is qualitatively different when its

overall composition is either much less or much greater than the composition at the top of
the miscibility gap, that is, when it produces an asymmetric spinodal. An example is the
composition, x1, that is indicated in Fig. 11.43. There are two principle differences.
First, when the composition is asymmetric the spinodal line is inside the miscibility gap.
When a solution of composition, x1, is quenched, it passes through a range of
temperatures in which it is metastable before penetrating the spinodal gap. One such
temperature is indicated by the upper dot on the vertical line at x1 in the figure. The
transformation mechanism in this range is the nucleation and growth of the solute-rich "
phase. Spinodal decomposition is only observed if the solution is cooled to a temperature
inside the miscibility gap at a rate fast enough to suppress nucleation until the spinodal
line is reached. The initiation curve for the transformation is like that drawn
schematically in Fig. 11.45. The nucleated transformation has a c-curve behavior, while
the spinodal transformation initiates as soon as the solution penetrates the two-phase
region.
ln()
spinodal decomposition
Fig. 11.45: Initiation kinetics for a solution like that with composition x1
Fig. 11.43. Spinodal decomposition is observed if the solution is quenched to suppress nucleation.
Second, the ultimate microstructure that results from spinodal decomposition is
different when the composition differs significantly from the symmetric value. The
development of the composition profile in an asymmetric decomposition is illustrated in
Fig. 11.46. The decomposition initially develops as a sinusoidal decomposition wave
that grows in amplitude (Fig. 11.46a). But since the average composition is close to one
boundary of the miscibility gap, the decomposition cannot be completed by the
symmetric growth of this wave. The result is shown in Fig. 11.46b; narrow, precipitatelike regions develop that are rich in solute concentration, and these grow to complete the
reaction.
As a spinodal like that in Fig. 11.46 develops in three dimensions it produces a
homogeneous distribution of precipitates through the bulk that is nearly indistinguishable
from that which would form by homogeneous nucleation.
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x
x
Fig. 11.46: Development of the composition profile in a asymmetric

spinodal decomposition. A low-amplitude spinodal wave
develops into discrete precipitates.
11.15.3 Spinodal decomposition to a metastable phase
Spinodal decomposition may cause the formation of a metastable precipitate
phase rather than an equilibrium transformation product. Fig. 11.47 illustrates a set of
thermodynamic relationships that cause this to happen. The free energy curves in the
figure are drawn for a temperature at which there are two equilibrium phases, and . If
a homogeneous solution that has a composition within the two-phase (+) field is
quenched to this temperature it is metastable with respect to nucleation of the phase.
However, the free energy curve contains a spinodal instability, marked by the shaded
region in the figure. If the composition of the quenched solution lies in the shaded
region it is unstable with respect to a spinodal decomposition that produces a metastable
phase, '. Since the kinetics of decomposition are more rapid than the kinetics of
nucleation, the metastable, ' phase forms preferentially. The ' phase has the same
crystal structure as the parent, and hence appears in the form of a dense distribution of
coherent precipitates.
'
'
Fig. 11.47: Free energy curves leading to formation of a metastable, coherent precipitate. If has a composition within the shaded
region, it is unstable with respect to ', as well as being
metastable with respect to .
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ln()
'
Fig. 11.48: Initiation kinetics for a transformation that may proceed by

nucleating an equilibrium phase, , or by spinodal decomposition to a coherent, metastable phase, '.
When a solution that has the behavior shown in Fig. 11.47 is cooled, the transformation kinetics tend to obey a relation like that shown in Fig. 11.48. Phase can
nucleate at small undercooling, but a quench suppresses this nucleation, and leads to the
spontaneous formation of a coherent, metastable phase, '.
11.15.4 Use of spinodal decomposition in materials processing
Spinodal decomposition has been intentionally used in materials processing to accomplish two different objectives. First, solutions with compositions well inside the miscibility gap are decomposed to create a microstructure that contains a fine admixture of
two phases of different composition. One particular example is in the processing of
magnetic materials in which it is desirable to have fine particles of magnetic phase
distributed through a non-magnetic, metallic matrix. If the solute-rich constituent of the
spinodal is magnetic while the solute-poor constituent is not, then the desired
microstructure can be created by spinodally decomposing a solution that is slightly rich in
solvent, so that the non-magnetic phase becomes the matrix. Another important example
is in the processing of ceramics. While nucleated transformations are often very difficult
to initiate in oxide ceramics, fine-grained two-phase microstructures can be made by
spinodal decomposition. This technique is used in the processing of a number of modern
ceramics.
The second use of the spinodal decomposition is to create a homogeneous
distribution of fine precipitates. In systems whose transformations resemble those shown
in Fig. 11.45 or 11.48, quenching into the spinodal gap produces a distribution of
precipitates in the interior of grains and, hence, provides an alternative to lowtemperature heat treatment as a method for achieving this microstructure.
11.16 ORDERING REACTIONS

The third important class of instabilities includes transitions that change the state
of order of the material while the crystal structure and overall composition remain the
same. The ordering transition was discussed in Section 8.4. The simplest ordering
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reaction is a transition from a disordered to an ordered state in a binary solution. In the

high-temperature, disordered state the atoms are randomly distributed over the sites of a
background crystal lattice. In the ordered state the sites of the crystal lattice are divided
into two sets, one of which is preferentially occupied by atoms of type A, while the other
is preferentially occupied by atoms of type B. Examples of substitutionally ordered
phases we have studied include the CsCl structure, which is a BCC-based structure with
one kind of atom at the corner sites and a second at the body-centered sites (see Fig.
11.49 below), and the Cu3Au structure, which is an FCC-based structure with one kind of
atom at the corners and a second at the face-centered sites of the unit cell (Fig. 11.51).
It is only possible to have perfect order when the composition of the solution is
the stoichiometric composition of the ordered phase (AB for the CsCl structure, A3B for
the Cu3Au structure), and when the temperature is so low that the fraction of anti-site
defects (A atoms on B sites) is negligible. In other cases we measure the degree of order
by the long-range order parameter, , which was defined in Section 9.4. To phrase the
most general definition of the order parameter in a binary solution let x be the atom
fraction of the component whose composition exceeds the stoichiometric value, xs, for
the ordered phase, and let x1 be the atom fraction of that component on the sites it
occupies in the ordered phase (x1 = 1 when all of these sites are filled). Then
x1 - x
= 1-x
11.65
When < 1 both types of sites contain a mixture of the two kinds of atoms. As
increases sites of type 1 become increasingly filled with atoms of type 1. However, even
when = 1 the compound is not perfectly ordered unless its composition is
stoichiometric. Even when all sites of type 1 are filled, if x xs there are additional
atoms of type 1 that must sit on sites that are appropriate to the other specie. That is,
there is a residual concentration of anti-site defects in the crystal.
11.16.1 Ordering reactions that are mutations
As we discussed in Section 8.4, there are two different kinds of ordering
reactions. In the first kind the structures of the ordered and disordered phases are so
closely related to one another that the reaction is a mutation; order happens
spontaneously when the disordered solution is cooled to a critical temperature, Tc. An
example of an ordering reaction that is a mutation is the transition from a disordered BCC
solution to a CsCl-ordered solution that occurs in brass (CuZn), which is shown in Fig.
11.49. At the critical temperature, Tc, order spontaneously appears.
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Fig. 11.49: Transition from disordered BCC to CsCl in CuZn. The

shading in BCC indicates random occupancy by Cu and Zn.
'
Tc
Fig. 11.50: Variation of the long-range order parameter with T in a mutation, like the disorder-order transition in -brass.
A phase transition that is a mutation is never nucleated since the parent phase is
never metastable. The transformation occurs spontaneously at the critical temperature,
Tc. The order parameter becomes finite at a temperature incrementally below Tc, and
increases in magnitude as the temperature is lowered further, as illustrated in Fig. 11.50.
11.16.2 First-order transitions that change the state of order
...
Fig. 11.51: The first-order transition from a disordered, FCC-solution to
the Cu3Au structure in Cu-Au.
The second kind of ordering transition includes transitions in which the structures
of the two phases are sufficiently different from one another that the transition is first-order. There is a well-developed theory, the Landau symmetry rules, that tell us how to
distinguish these transformations, but the development of this theory is beyond the scope
of this course. An example is the transition from a disordered solution to a Cu3Au
structure in Cu-Au, which is illustrated in Fig. 11.51.
When the ordering reaction is first-order there is a discontinuous change in the
equilibrium value of the order parameter at the equilibrium transformation temperature,
as described in Section 9.4. Moreover, it is possible to cool the disordered solution, or
heat the ordered solution, into metastable states beyond the equilibrium transformation
temperature. This behavior is illustrated in Fig. 11.52, which shows the variation of the
equilibrium value of the order parameter near the transition temperature, T0.
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= metastable ordered phase
'
= metastable disordered phase
T0
Fig. 11.52: Variation of the order parameter for a first-order ordering

reaction, showing the ranges of metastability near the
equilibrium transition temperature, T0.
As indicated in Fig. 11.52 the range of metastability is limited. If the disordered
phase is cooled below the transition temperature at a rate that is rapid enough to suppress
nucleation, the material becomes unstable with respect to the spontaneous appearance of
long-range order when the undercooling becomes great enough.
The instability temperature for the ordering reaction varies with composition, and
can be plotted on the phase diagram as is done in Fig. 11.53. This figure shows a simple
prototype reaction in which a disordered solution, , has a first-order transition to an ordered phase, . The phase diagram is like that shown in Fig. 8.35; the equilibrium phase
field of the ordered phase has a teardrop shape whose top defines a congruent (constant
composition) ordering transformation from the parent phase. The congruent point is at,
or very close to, the stoichiometric composition for the ordered phase (Cu3Au in the
copper-gold case). The line in the phase diagram indicates the onset of instability. If a
disordered solution is cooled to the instability line, it spontaneously orders, insofar as
its composition allows, to produce a homogeneous ordered phase.
x1
T
x2
+
A
Fig. 11.53: A section of the equilibrium phase diagram of a system that

contains an ordered phase. The disordered solution is
unstable when the temperature falls into the lightly shaded
region.
The transformation behavior of a system like that shown in Fig. 11.53 changes
with the composition of the phase. In particular, the transformation behavior at the
stoichiometric composition (x2 in the figure) is qualitatively different from that at a
significantly off-stoichiometric composition, such as the composition x1 in the figure.
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11.16.3 Ordering at the stoichiometric composition
T0
ln()
nucleated
Ti
spontaneous
Fig. 11.54: Kinetic diagram for ordering at the stoichiometric

composition. The transformation is nucleated at T > Ti, but
becomes spontaneous at the instability temperature, Ti.
First consider transformation at the stoichiometric composition, indicated by x2 in
Fig. 11.53. In this case the solution becomes metastable with respect to congruent nucleation of the phase as soon as its temperature falls into the region. It remains
metastable until the temperature drops below the instability line shown in the figure. If
nucleation has not happened when this point is reached the system spontaneously
becomes ordered; A-atoms spontaneously move to A-sites and B-atoms to B-sites.
The kinetic diagram for the stoichiometric reaction is like that shown in Fig.
11.54. The nucleated transformation becomes possible when the temperature drops
below T0. If the transformation has not happened when the temperature reaches Ti, the
instability temperature, then a homogeneous ordering reaction initiates spontaneously.
11.16.4 Ordering at an off-stoichiometric composition
The transformation behavior is qualitatively different when the composition is
off-stoichiometric, for example, the composition x1 in Fig. 11.53. To understand the
transformation behavior in this case it is useful to consider the free energy curves of the
disordered, , and ordered, , phases, which change with temperature roughly as shown
in Fig. 11.55. As the temperature is lowered the free energy curve for the phase drops
relative to that of the phase. In addition, the composition at which the -phase
becomes unstable (the solid curve in Fig. 11.53) decreases. This composition is indicated
by the termination of the free energy curve in Fig. 11.55.
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T1
g
T2 < T1
x1
x
Ti
x1
x
x1
x
Fig. 11.55: Possible form of the free energy curves of the and phases
in Fig. 11.53 as the temperature decreases. The dot marks a
disordered solution with composition, x1.
When a solution of composition, x1, is cooled to a temperature just inside the twophase region the free energy curves appear like those shown in Fig. 11.55a. The system
is metastable, but can only transform by nucleating a solute-rich phase. If the sample is
cooled to a lower temperature at a rate that is fast enough to suppress nucleation of the
equilibrium phase then becomes metastable with respect to the formation of a non-stoichiometric ordered phase, , that has the same composition, as illustrated in Fig. 11.55b.
Hence congruent nucleation becomes possible. However, as the temperature drops the
composition at which the disordered solution becomes thermodynamically unstable decreases, so the termination of the free energy curve of the phase moves closer to x1.
Finally, at the instability temperature, Ti, an phase of composition, x1, becomes
unstable with respect to spontaneous order into the phase, as illustrated in Fig. 11.55c.
If the solution is cooled to Ti quickly enough to suppress congruent nucleation, the
system orders spontaneously at Ti.
ln()
incongruent
nucleation
Ti
congruent
nucleation
spontaneous order
Fig. 11.56: Kinetic diagram for the ordering of an off-stoichiometric disordered solution.
The kinetic diagram for a transformation at composition, x1, appears as shown in
Fig. 11.56. Slow cooling leads to nucleation of the equilibrium ordered phase, more
rapid cooling produces congruent nucleation of an off-stoichiometric ordered phase, and
quenching leads to spontaneous order.
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Note that when an off-stoichiometric solution of composition like x1 transforms

through congruent nucleation or spontaneous ordering the product of the transformation
is a non-equilibrium ordered phase. To achieve equilibrium the homogeneous reaction,
, must be followed by a second reaction, + , in which islands of disordered
solution reform out of the ordered phase.
Many of the materials that are coming into use in advanced engineering systems
are ceramics or intermetallic compounds with complex, ordered structures. These often
have multiple ordered structures that are, in practice, connected to one another by
congruent ordering reactions. Largely for this reason, ordering reactions and ordering
instabilities are becoming increasingly important in the processing of modern materials.
Ordering reactions can also be exploited for the control of microstructure. This is
particular true in solids with very low diffusivities. If diffusion is very slow, as it is in
many ceramic and intermetallic phases, then decomposition is easily suppressed and nonstoichiometric ordered phases can be made and retained almost indefinitely. Hence the
basic crystal structure of the compound can be controlled by adjusting the cooling rate.
When the diffusivity is higher, it is possible to engineer the microstructure of a
two-phase mixture of ordered and disordered phases by controlling the reaction sequence
that leads to the equilibrium state. A solution like that shown in Fig. 11.56 can be
brought to equilibrium by two very different paths that may lead to very different final
microstructures. If the disordered parent solution is cooled slowly, it decomposes by
nucleation of the equilibrium ordered phase. The reaction is + . If the sample is
cooled quickly it orders before decomposing. The reaction is a two-step one in which
+ .
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Chapter 12: Environmental Interactions

In lodgings frail as dew upon the reeds
I left you, and the four winds tear at me
- Murasaki Shikibu, "The Tale of Genji"
12.1 INTRODUCTION
In the last few chapters we have considered the changes that occur within a
material when we alter its temperature or chemical composition. In the present chapter
we consider the changes that are brought about in a material when it reacts with its
environment. The important environmental interactions are of three types. The first type
includes reactions that change the microstructure of the material near the surface by
adding heat or chemical species from the environment. These include the surface
hardening reactions that are widely applied to structural materials and the doping
reactions that control the properties of semiconductors. The second type includes
chemical reactions between the metal and its environment that form compounds at the
interface. There are many important reactions of this type. We shall specifically
consider the oxidation reaction, since it is both important in engineering and illustrative
of the mechanisms that govern interfacial reactions.
The third type includes
electrochemical reactions, in which the chemical reaction at the interface is assisted by
electric currents so that it has an appreciable rate at low temperature. The most important
electrochemical reaction is aqueous corrosion, which is responsible for the gradual
deterioration of metallic structures that are exposed to water, soil or moist air.
12.2 CHEMICAL CHANGES NEAR THE SURFACE

The first class of environmental interactions we shall consider are those that
change the microstructure of the solid immediately beneath its surface. It is often
desirable to do that to control the mechanical, chemical or electrical properties of the
material near the surface. Rapid thermal treatments are used to change the phase, grain
structure or chemical distribution near the interface. Chemical diffusion or ion
implantation is used to change the chemical composition near the surface.
12.2.1 Thermal treatment
To control the microstructure of the layer of material just beneath a solid surface
it is useful to have a way of heating that particular material without significantly heating
the interior. It is difficult to do this because heat is conducted so rapidly in most
materials that heating the surface quickly raises the temperature in the interior. The
methods that are useful for the thermal treatment of surfaces create intense, local heat
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sources in the material immediately beneath the surface. The possible heat sources
include electrical currents and locally absorbed beams of light or high-energy electrons.
These can cause local heating at the surface that is so rapid that a high temperature is
reached before heat can be conducted away. The thermal conductivity of the solid then
becomes an advantage, since the hot surface layer is rapidly quenched by heat flow into
the bulk, often freezing it in a non-equilibrium microstructure that has desirable
properties. The common methods of rapid thermal treatment are induction heating, laser
surface processing, and electron beam processing.
Induction hardening
If a high-frequency alternating current is passed through a coil located near the
surface of a metal it induces electrical currents. These raise the temperature by Joule
heating. If the coil is small and close to the surface the induced current does not
penetrate very far into the interior. If the induction current is shut off after a short time,
the heated layer cools rapidly as heat flows into the interior.
hardness
case
depth
Fig. 12.1:
x
The variation of hardness with depth below the surface for a
case-hardened part.
Local induction heating is a common method for producing a hard, wear-resistant

surface on steel parts, such as gears, shafts and bearing races. A layer of material
adjacent to the surface is heated to a temperature above that at which the low-temperature
BCC (ferrite) phase reverts to the high-temperature FCC (austenite) phase, and then
quenched to form a layer of fresh martensite. The fresh martensite layer is very hard
because of its high defect density. The induction hardening of a typical carbon steel
produces a hardness profile like that shown in Fig. 12.1. The rapid drop in hardness
defines the limit of the martensite layer, and measures what is called the "case depth" of
the hardened part. The manufacturing specifications for hardened gears set both the level
of surface hardness and the case depth over which some minimum hardness must be
maintained.
Laser surface processing

Laser surface processing is an even more efficient method of thermal treatment.
In this method the surface is subjected to an intense pulse of coherent light from a highpower laser. The frequency of the light is chosen so that a high fraction of the incident
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energy is absorbed within a short distance of the surface. The almost instantaneous
absorption of the optical energy of the laser beam by a small volume of solid raises its
temperature dramatically. Commonly a layer of material parallel to the surface is
actually melted by the beam. However, since the melted layer is small in thickness, it is
very rapidly quenched back into the solid state as heat flows into the bulk. A significant
advantage of laser surface treatment is the thin layer that is processed; properly designed
laser treatments can create treated layers whose thickness is on the order of microns.
Laser surface processing is sometimes used simply to modify the microstructure
of the surface layer. Passing a laser beam over the surface of a metal may create a thin
surface layer with a highly defective microstructure that has exceptional hardness, and,
hence, good wear resistance. Laser surface treatment of a semiconductor, such as silicon,
can produce a thin amorphous layer that has useful electrical properties.
Lasers are also used to make surface layers with combinations of composition and
microstructure that are not easily obtained in other ways. For example, elements such as
carbon, phosphorous and boron have very limited solubility in solid steel, but are much
more soluble in the liquid. If a thin layer of carbon or phosphorous is deposited onto the
surface of a steel and then treated with a laser pulse, the carbon or phosphorous dissolves
into the surface layer while it is molten, and is trapped there by rapid solidification. The
result is a very highly doped surface layer with very high hardness. It may also be amorphous in its structure. Among other potentially useful properties, amorphous surface
films on metals often lead to exceptional corrosion resistance. The uniformity of an
amorphous coating eliminates the local galvanic couples that promote corrosion of
normal metal surfaces.
Electron beam treatments

High-energy electron beams are also used for surface treatments. When an
electron beam strikes a metallic conductor, its energy is absorbed in the layer
immediately beneath the metal surface, so the beam has nearly the same effect as a laser
pulse. Electron beams are advantageous in that they easier and cheaper to create than
intense laser pulses, and provide a more efficient energy transfer to the metal. However,
it is difficult to produce electron beams with the short, intense pulses that are possible
with lasers, so it is more difficult to confine the heating to the immediate surface region.
High-energy electrons have complex interactions with semiconductors; laser processing
is usually more controllable and useful for these materials.
12.2.2 Diffusion Across the interface
The simplest method for changing the composition near the solid surface is by
diffusion from the environment. Diffusion can be induced by heating the solid in a vapor
that contains the solute or by plating the solute onto the surface and maintaining a high
temperature until it diffuses in. The two processes are roughly equivalent. In the former
case the surface concentration is fixed by adsorption of solute from the vapor phase. In
the latter, it is fixed by the composition of the deposited surface film.
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The concentration profile

The solute concentration at a distance, x, below the surface at a time, t, can be
found by solving the diffusion equation (Fick's Second Law; Chapter 9):
2
c(x,t)
=
D
c(x,t)
t
x2
12.1
where D is the diffusion coefficient for the solute. If the solute concentration at the
surface is fixed (c = c0 at x = 0), the initial concentration in the solid is negligible, and the
solid is very large compared to the effective diffusion distance, then the solution to
equation 12.1 is
c(x,t) = c01 - erf
2 Dt
12.2
where erf() is a function that is called the error function, and has the value
erf() =
0
e- u
du
12.3
The error function is tabulated in most compilations of mathematical functions.

c0
Fig. 12.2:
increasing
time
x
Successive profiles for diffusion from the interface.
The concentration profile is plotted for several values of the time in Fig. 12.2.
The equation
x = 2 Dt
12.4
gives the value of x at which the concentration is c = c0[1 - erf()] at time t, so the thickness of the layer that has been doped to a given concentration increases with the square
root of the time. Since erf() to within a few percent when is less than about 0.75,
the concentration profile satisfies the simple equation
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c
c0
1-
x
2 Dt
12.5
for c/c0 greater than about 0.25. Equation 12.5 can be used to set the temperature and
time for a process that is intended to insure a minimum dopant concentration within a
pre-selected depth. At the mean diffusion distance, x = 2Dt , the solute concentration
is approximately 0.3c0.
Surface diffusion has the advantage of being a relatively simple and inexpensive
processing step. Its principle disadvantages are that it produces a steep concentration gradient rather than the flat concentration profile that is often desirable, and requires a relatively high temperature so that diffusion is reasonable fast.
Surface hardening: carburizing and nitriding

A common use of diffusion from the vapor is in the hardening of metal surfaces
through carburizing and nitriding. The most common method of carburizing a steel part
is to pass the part through a furnace that contains an atmosphere from which carbon
diffuses into the metal. The carbon hardens the steel in one of two ways, depending on
the temperature at which the carbon is added. If the carburizing temperature is below the
temperature at which the steel reverts from the BCC to the FCC phase (the austenitization
temperature), then the carbon is added to a microstructure that is more or less fixed.
Carbon hardens the steel by an amount that is roughly proportional to the carbon
concentration, but is limited by the very low solubility of carbon in the ferritic phase; if
the carbon concentration exceeds the solubility limit it precipitates into carbides that form
primarily on the grain boundaries and do not increase the hardness very much further. In
the usual case carbon is added at high temperature where the steel has the FCC austenite
phase. The FCC phase has a relatively high carbon solubility. On subsequent cooling, the
austenite transforms to martensite with carbon trapped at high concentration. This
martensite is very hard because of its high density of crystal defects, and forms a
hardened surface layer. The hardness of the carburized layer is roughly proportional to
the fraction of martensite and varies with distance beneath the surface roughly as shown
in Fig. 12.1.
Nitrogen is an alternative to carbon for surface hardening. Nitrogen also has a
very low solubility in ferritic steel, but has an advantage over carbon in that excess
nitrogen forms hardening precipitates within the ferrite grains, particularly in steels that
are alloyed with Mo, Cr or Al. For this reason steels can be nitrided at relatively low
temperature where they retain the ferritic structure. In addition, nitrogen has a high
solubility in the FCC phase of iron (austenite) and is, therefore, particularly useful in
hardening high-alloy stainless steels that retain the FCC structure at room temperature.
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Semiconductor doping
As we shall discuss below, the electrical properties of semiconductors are controlled by adding small concentrations of electrically active impurities that act as donors
or acceptors of electrons. Almost all semiconducting devices are based on semiconductor
junctions, which are surfaces across which the nature of the conductivity changes from ntype conduction based on excess electrons in the conduction band from donor impurities
to p-type conduction based on the holes in the valence band from acceptor impurities. A
simple example is diagrammed in Fig. 12.3. To create these devices it is necessary to introduce controlled distributions of selected impurities.
n
Fig. 12.3:
A semiconductor with an n-p-n junction near its surface. The

n- and p-type regions are doped with donor and acceptor impurities, respectively.
A typical method for doing this is diagrammed in Fig. 12.4, where we have used
silicon as a specific example. A thin layer of oxide is plated over the silicon surface by
reacting with oxygen. Using techniques that will be described in a later chapter, the
oxide is etched away over the region that is to be doped. The crystal is then exposed to
an atmosphere that contains the dopant impurity, which adsorbs or deposits onto its
surface. The sample is held at a temperature high enough to stimulate diffusion into the
silicon, but low enough that diffusion through the oxide layer is negligible. The result is
a distribution of dopant through the surface region beneath the cut in the oxide layer, as
illustrated in Fig. 12.4b. If the cut in the oxide layer is large compared to the mean
diffusion distance the concentration profile well inside the cut is the one-dimensional
profile given by eq. 12.2. In any case, the diffusion profile varies with distance into the
solid roughly as illustrated in Fig. 12.2.
Fig. 12.4:
(a)
(b)
Locally doping a semiconductor. (a) An oxide layer is etched
to expose surface and the dopant is deposited. (b) Dopant is
diffused in to create a diffuse doped region and the oxide removed.
12.2.3 Ion implantation

Ion implantation provides a more direct means for controlling the composition beneath the surface. In this technique the dopant species is ionized and accelerated toward
the solid surface by an electric field. The kinetic energy of ions causes them to penetrate
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a short distance into the solid before decelerating and embedding. The mean penetration
distance is fixed by the kinetic energy, which can be controlled by setting the potential
through which the ions are accelerated. Ion implantation ordinarily leads to a
composition profile like that shown in Fig. 12.5; the profile has a Gaussian form that is
centered about the mean penetration distance, .
Ion implantation has three advantages over diffusional doping. First, virtually any
species can be implanted by ionization, including those whose low diffusivities or low
solubilities make them difficult to add by diffusional doping. Second, it is not necessary
to heat the material before implantation, so dopants can be implanted into crystals that
would degrade if they were heated to the temperatures required for diffusional doping.
Third, ion implantation creates a very different initial composition profile than diffusional
doping. If the material is heated slightly to diffuse the ion after implantation, the
Gaussian profile of implanted ions spreads to become relatively flat, as illustrated in Fig.
12.5. The result is a much more uniform composition over the doped region. This is a
particularly desirable feature in the manufacture of semiconducting devices, which
should have relatively constant electrical properties within each separately doped region.
ion implantation
diffusion
Fig. 12.5:
Typical dopant profiles produced by ion implantation, and by

impantation followed by diffusion.
The disadvantages of ion implantation include the relative complexity of the

equipment required, which makes it expensive to use ion implantation for the surface
treatment of large metal parts, and the physical damage that is done by the ions as they
burrow into the solid at high energy, which causes defects that degrade the electrical
properties of semiconductors. The latter problem requires that ion implantation processes
for semiconductors be carefully designed, by adjusting the kinetic energy of the ions,
their implantation rate, and subsequent annealing treatments, so that residual defects are
held within tolerable levels.
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12.3 CHEMICAL REACTIONS AT THE SURFACE: OXIDATION

The second class of reactions that occur between a solid and its environment are
chemical reactions that cause the formation and growth of new compounds at the
interface. The most familiar of these is oxidation. If a typical metal or semiconductor is
heated to high temperature in air an oxide forms on its surface that grows until the
material is consumed. We shall focus on the oxidation reaction because of its familiarity,
its importance in engineering, and its value as a prototypic example of compound
formation at an interface. However, oxidation is only one of many interfacial reactions
that are important in the processing and use of engineering materials, and is a particular
example of a reaction at a solid-vapor interface. Reactions that occur at solid-solid
interfaces have distinct features that should also be appreciated.
12.3.1 Thermodynamics of oxidation
When a metal or elemental semiconductor is exposed to an atmosphere that
contains strong oxiding agents such as oxygen, sulfur or chlorine, the solid and gas react
at the interface to form a scale of oxide, sulfide or chloride. If the reactant is oxygen the
chemical reaction is
y
xM + 2 O2 = MxOy
12.6
where M is the solid MxOy is the stoichiometric formula for the oxide. The free energy
change per mole of oxygen consumed is
2
2x
g = y (MxOy) - y (M) - (O2)
12.7
The chemical potential is usually written in the form

(T,P,c) = 0(T) + RTln(a)
12.8
where 0 is a function of T (we assume atmospheric pressure), and a, which is called the
activity of the species, gives its dependence on the composition, c. Eq. 12.8 is, in fact,
the definition of the activity. The activity is a simple function of the composition in four
limiting cases: (1) if the specie is pure (c = 1), then a = 1 and 0 is its molar Gibbs free
energy in the pure state; (2) if the specie is the solvent of a dilute solution (c 1), then a
= c and 0 is the molar free energy in the pure state (this is called Raoult's Law); (3) if
the specie is a gas in an approximately ideal gas mixture then 0 is its free energy in the
pure state and a = p, its partial pressure in the gas; (4) if the specie is a solute in a dilute
liquid or solid solution (c << 1) then a = c, where is called the activity coefficient, and
has a constant value when c is small (this is known as Henry's Law).
If the oxidizing solid, M, is nearly pure and the oxide, MxOy, is formed in the
solid state, equation 12.7 can be rewritten
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g = g0 - RT ln(pO2 )
12.9
where g0 is called the standard free energy of formation of the oxide,

2
2x
g0 = y 0(MxOy) - y 0(M) - 0(O2)
12.10
and pO2 is the partial pressure of oxygen in the gas. When the reaction is in equilibrium
the oxygen partial pressure is given by
g0 = RT ln(pO2 )
12.11
when the partial pressure exceeds this value the sample oxidizes.
0
-200
Cu O
2
FeO
NiO
-400
Cr O3
2
g (J/mole)
SiO2
-600
Al O3
-800
-1000
200
400
600
800
1000
T (C)
Fig. 12.6:
Standard free energies of formation of selected oxides.
The standard free energy of formation of several common oxides are plotted as a
function of temperature in Fig. 12.6. g0 is negative for all common structural metals
and elemental semiconductors. The only notable exceptions are the noble metals, Au, Ag
and Pt, whose oxidation resistance is largely responsible for their economic value.
Two features of the data shown in Fig. 12.6 may be surprising. First, the common
metals have very negative values of g0 at low temperatures, which suggests that they
should oxidize rapidly in air at room temperature. Second, g0 increases (becomes less
negative) as the temperature rises; the thermodynamic driving force for oxidation
decreases with temperature. The engineering behavior of structural metals and alloys is
the opposite of this. Metals do not oxidize appreciably at room temperature, but do
oxidize at high temperature at a rate that increases with the temperature. This behavior
shows that the oxidation that is of practical concern is controlled by the kinetics of the
process.
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12.3.2 The kinetics of oxidation

Oxidation occurs by one of three mechanisms that lead to the three distinct kinetic
relations illustrated in Fig. 12.7. In the most basic reaction the oxide grows as a
continuous film that thickens through the reaction of the metal and the oxide at the oxidevapor interface or, less commonly, at the metal-oxide interface. The rate of this reaction
is limited by the rate at which the reactants can diffuse through the film, and obeys the
parabolic relation
m = k t
12.12
where m is the mass of metal oxidized in time t. The second mechanism, which is responsible for rapid oxidation at high temperature, occurs when the stresses that are developed in the growing film cause it to crack or spall off of the surface as it grows. The recurring damage to the film continuously exposes fresh surface to the oxidizing environment, and the rate of oxidation is linear:
m = k't
12.13
The third mechanism applies to very thin films, particularly those that form at low
temperature. It remains poorly understood. However, it is clear that when a film is only
a few nanometers thick its growth is strongly affected by inhomogeneous charge
distributions that develop as the metal and oxygen ionize at the film surfaces. The
electric field set up by these charges promotes the diffusion of ionic species. The result is
a logarithmic behavior in which the oxidation is given by an expression of the
approximate form
m = k"ln(Bt + 1)
12.14
Fig. 12.7:
ln(t)
(a)
(b)
(c)
The three common kinetic relations for interfacial reactions:
(a) parabolic growth; (b) linear growth; (c) logarithmic
growth.
Parabolic oxidation
To understand parabolic oxidation, assume that a thin oxide film has formed, as
shown in Fig. 12.8, and consider the sequence of events that must happen at the atomic
level in order for it to grow. As shown in the figure, oxygen molecules (O2) are absorbed
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onto the surface and dissociate into adsorbed oxygen atoms. To grow the film, these
must ionize and react with ionized atoms from the underlying metal. In most cases the
reaction occurs at the outer surface of the oxide layer. Metal atoms ionize at the inner
surface of the oxide. The metal ions (M++) diffuse into the oxide film, creating a
diffusion current of ions to the surface. At the same time, electrons are transported to the
surface as an electrical current; most metal oxides are at least semiconducting and permit
some current flow. Both electrons and ions participate in the oxidation reaction at the
outer surface:
M++ + 2e- + O MO
O2
O=
2e-
12.15
MO
M
++
oxide
metal
Fig. 12.8:
The typical mechanism of oxide film growth. Oxygen atoms

adsorb, dissosciate, ionize by accepting electrons from the
metal, and grow oxide by combining with ions from the
metal.
The rate-limiting step in the reaction described above is the diffusion of metal
ions through the oxide film. Since the mean diffusion distance of the metal ions is
proportional to Dt , where D is the ion diffusivity, the film thickness, , varies with
time as
= A Dt
12.16
where A is a constant. The total mass of metal consumed is simply proportional to the
film thickness; hence
m = k t
12.12
which is the parabolic growth law. The rate of oxidation, the mass of metal consumed
per unit time, is
dm
k
=
dt
2 t
12.15
which decreases monotonically with the time.
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The temperature dependence of the oxidation rate is primarily due to its

dependence on the diffusivity. The rate constant, k, varies with temperature as
QD
k = Aexp- 2kT
12.16
where QD is the activation energy for diffusion of the rate-limiting species, usually the
metal ion. The rate of oxidation is very low at low temperatures where the diffusivity is
negligible. The rate increases exponentially with (1/T), and becomes significant when
the temperature is high enough for solid state diffusion to proceed at a reasonable rate.
To understand the rate of film growth in a particular case one must identify the
rate-controlling specie and understand its diffusion mechanism. In most cases the fastdiffusing species is the metal cation. It is useful to divide the oxides that are controlled
by cation diffusion into two groups: metal-deficit oxides (called p-type oxides after their
semiconducting characteristics) and metal-excess oxides (n-type oxides). The two types
of oxide are illustrated in Fig. 12.9. Metal-deficit oxides contain point defects of the
Shottky type (described in Chapter 4) in which paired vacancies appear on the cation and
anion lattices. Metal ions diffuse by cation-vacancy exchange on the cation lattice, and,
since the cations are more mobile, govern the rate of oxide growth. Given the presence
and mobility of cation vacancies, the metal content in these oxides is, ordinarily, a bit
below the stoichiometric value, giving them a p-type electrical character. Common
oxides that fall into this class include Cr2O3, MnO, FeO, NiO and Cu2O.
= cation (+)
= anion (-)
= vacancy
(a)
...
Fig. 12.9:
(b)
Defects in oxides. (a) Shottky defect: paired vacancies on
anion and cation sites. (b) Frenkel defect: cation interstitial
and vacancy.
Metal-excess oxides contain point defects of the Frenkel type (Chapter 4), in
which a cation interstitial is paired with a cation vacancy. Metal ions diffuse as highly
mobile cation interstitials. In these oxides there is ordinarily a slight excess of interstitials that are injected by ionization at the oxide-metal interface, hence these oxides
tend to be n-type semiconductors. Common metal-excess oxides include BeO, MgO,
CaO, ZnO, and CdO.
A third group of oxides form at a rate that is governed by the diffusion of oxygen.
Most of these are oxides that have an excess of oxygen vacancies due to multiple valance
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of the cation. The classic example is ZrO2. Zr can have valence 2 or 4, and ZrO2 films
have high concentrations of oxygen vacancies with the missing charge balanced by Zr
cations with valence 2 rather than 4. The high concentration of oxygen vacancies has the
consequence that oxygen diffusion controls the rate of film growth, and the oxide
thickens at the metal-oxide interface rather than at the oxide-vapor interface.
Whatever the dominant ion, almost all oxide films that form at moderate to high
temperature obey parabolic growth kinetics during the initial stages of their growth.
Since the rate of oxidation decreases monotonically with time, these films are protective;
they seal the surface from catastrophic oxidation.
Linear oxidation
A parabolic oxidation rate is maintained as long as the oxide film remains intact
and well-bonded to the metal surface. However, in most cases of high temperature
oxidation the film does not remain intact. The reason is that the oxidation reaction
involves a volume change. The volume change per mole of oxide produced is described
by the Piling-Bedworth ratio
vO
P = nv
12.17
where vO is the molar volume of the oxide, vM is the molar volume of the metal, and n is
the number of moles of metal consumed to create a mole of oxide.
(a)
(b)
...
Fig. 12.10: Modes of film failure. (a) Film cracks due to a negative volume change. (b) Film spalls due to a positive volume
change.
If P < 1, as it is, for example, for the oxides of most alkali metals, then the volume
of the oxide formed is less than that of the metal consumed. The oxide can only be fit
onto the metal surface by stretching it in tension. It can be shown that the tension in the
film increases with its thickness. When the film is very thin the tension is sustainable,
but when it grows to a critical thickness, the tension exceeds the breaking strength of the
film and it cracks, exposing fresh surface to the oxidizing atmosphere.
The film also fails if P is much greater than 1, as it is in the case of iron oxides.
When P > 1 the stress in the film is compressive. As the film grows, the compressive
stress increases. Some oxides are sufficiently deformable that the compressive stresses
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can be relieved by plastic flow. Others are not. If the compressive stress cannot be
relieved by plastic flow, it accumulates until the oxide fails, usually by losing cohesion at
the interface and spalling away from the surface, as shown in Fig. 12.10(b). This process
is responsible for the flakes of oxide that appear on the surface of oxidized iron. The
failure of the oxide film exposes fresh surface to the oxidizing atmosphere, and increases
the oxidation rate.
In either case the local failure of the oxide film periodically exposes fresh surface
to the oxidizing medium. The fresh surface oxidizes through the formation of a film that
grows until it also fails. The net result is an almost linear corrosion rate, like that shown
in Fig. 12.9(b).
Several other mechanisms can also lead to failure of the protective film, and to an
almost linear oxidation rate. The most spectacular case is called catastrophic oxidation,
and occurs when the oxide film melts. Relatively low-melting oxides are formed on V,
Mo, Bi and Pb. A molten oxide layer permits the diffusion of oxygen to the metal
surface, producing a very rapid, linear oxidation. In other systems, such as Al, Si and W,
the oxide is volatile at high temperature. These metals develop a steady-state oxide film
whose thickness is such that the rate of oxide formation by ion diffusion to the surface is
just equal to the rate at which oxide is removed by evaporation. Once steady state is
achieved, the oxidation is linear. A final case includes metals that form porous oxide
films, as Ni does at high temperature. These are metals that form "metal-deficit" oxides
in which diffusion occurs by a vacancy mechanism on the cation sublattice. The net flux
of cations (M++) to the oxide surface produces a counterflow of cation vacancies toward
the metal surface. At high temperature the vacancy flux may becomes sufficient to create
local vacancy supersaturations at imperfections in the film that nucleate voids. This
process can lead to a porous oxide film. The surfaces of the pores provide easy diffusion
paths that increase the oxidation rate, and may result in linear oxidation if the porosity is
severe.
Linear oxidation is responsible for the relatively rapid oxidation of most metals at
high temperature. To control high-temperature oxidation it is critically important to
prevent linear oxidation by ensuring the retention of a coherent oxide film.
Logarithmic oxidation
Logarithmic oxidation, like that shown in Fig. 12.9(c), governs the very thin oxide
films that form on metals that are exposed to air at low temperature. This mechanism
governs behavior under conditions where the oxidation rate is almost negligible.
The mechanism of logarithmic oxidation remains controversial. There are several
competing theories, any one of which may pertain to a particular oxide system. All are
based on the fact that film growth requires the transport of both ions and electrons. Since
the ions and electrons move independently, charge inhomogeneities build up in the film
and govern the rate of oxidation.
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The simplest and, arguably, most plausible theory of logarithmic growth is due to
Mott and Cabrera. It is based on the observation that electrons are much more mobile
than ions. It is, therefore, possible to develop a layer of ionized oxygen at the oxide-vapor interface. This produces an excess negative charge at the oxide surface that is
balanced by excess positive charge at the metal surface (Fig. 12.11) The charge
separation creates an electric field within the film, which can be very intense if the film
is only a few nanometers thick. The electric field imposes a force on the cations and
increases their diffusion rate (the enhancement of diffusion of a charged species in the
presence of an electric field is known as electromigration). However, the field strength
decreases with film thickness, and the effective diffusivity of the cations falls back to the
field-free value when the film thickness exceeds about 100 nm. The result is a
logarithmic rate of film growth.
O=
O=
++
O=
++
O=
O=
O=
O=
O
oxide
E
2e- ++ M ++ ++
++
M
M
M
metal
...
Fig. 12.11: Mechanism of logarithmic growth. Oxygen and metal ions
are created at the two interfaces. The resulting electric field,
E, raises the rate of cation diffusion through the film.
Since the cation diffusivity in most oxides is negligible at room temperature,
when a metal is exposed to ambient air logarithmic growth leads to the formation of a
very thin film that essentially ceases to grow after it has reached a few nanometers in
thickness. At higher temperature, logarithmic growth governs the initial kinetics of film
formation, but growth becomes parabolic as soon as the film thickness exceeds a few
nanometers.
12.3.3 Protecting against oxidation
Protective films
The principal requirement for oxidation resistance is the presence of an intact, coherent oxide film. Some materials, such as Al and Cr, form such films naturally and successfully resist oxidation until the temperature becomes so high that the oxide loses
stability. Most other materials form protective films at low temperature, where low
cation diffusivity limits film thickness, but lose the protective layer at higher
temperatures where the film cracks, spalls or becomes porous. It is often possible to
increase the oxidation resistance of these materials by alloying with species that are
incorporated into the oxide film and help preserve its integrity.
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An alloy addition will be effective if it changes film growth in either of two ways.
First, an alloy addition that lowers the diffusion rate through the film increases the time
required for the film to grow to the thickness at which film stress causes failure. Second,
an alloy addition that improves the geometric fit between the film and the substrate
reduces stresses and permits significantly greater film growth before failure.
The most common example of a beneficial alloy addition is Cr in Fe. Fig. 12.12
illustrates the variation of the parabolic rate constant for corrosion of Fe-Cr alloys at
1000C as a function of Cr content. The addition of 10% Cr lowers the rate constant by
more than four orders of magnitude. The reason is the preferential incorporation of Cr
into the oxide film, which produces a mixed oxide with a high content of Cr2O3. The
low cation diffusivity through Cr2O3 decreases the parabolic rate constant. The parabolic
rate constant decreases monotonically with Cr content up to about 18% Cr, by which
point the initial oxide film is essentially pure Cr2O3. At the same time, the Cr-bearing
film has improved coherence with the substrate. Steels that contain more than 10.5% Cr
are called stainless steels because of their excellent oxidation and corrosion resistance.
Al alloy additions have a similar beneficial effect; in this case the protective film is
Al2O3.
ln (k)
10
15
20
Cr (wt%)
Fig. 12.12: The influence of Cr on the parabolic rate constant for

oxidation of steel.
While significant additions of Al and Cr replace the oxide film with one that has a
significantly lower growth rate, other alloy additions influence the oxidation rate by
changing the cation diffusivity in the original oxide film. The alloy additions that have
this effect decrease the concentration of the defects that are responsible for diffusion.
In metal-excess (n-type) oxides the diffusing species are interstitial cations, such
as
interstitials in ZnO (Fig. 12.9(b)). Since these interstitials produce a local excess
of positive charge, their formation energy is reduced by the addition of cations that have
lower valence, and is increased by the addition of cations with higher valence. It follows
that the concentration of interstitials increases with the concentration of low-valence
solutes, and decreases with the concentration of high-valence solutes. Hence a small
alloy addition of Li, which ionizes to Li+, increases the parabolic rate constant for the
oxidation of Zn, while a small addition of Cr, which ionizes to Cr+3, decreases it.
Zn++
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ln (k)
10
15
20
Cr (wt%)
Fig. 12.13: The influence of Cr on the parabolic rate constant for

oxidation of Ni.
These species have the opposite effect on metal-deficit (p-type) oxides, such as
NiO. Cations diffuse through these oxides by exchanging with vacancies. Since cation
vacancies cause an excess of negative charge, their concentration is increased by substitutional cations that have higher valence, and decreased by cations of lower valence.
Hence a small alloy addition of Li decreases the rate constant for oxidation of Ni, while a
small addition of Cr increases it. This effect explains the anomalous oxidation behavior
of Ni-Cr alloys, which is illustrated in Fig. 12.13. The parabolic rate constant for
oxidation of Ni at 1000C increases with the addition of Cr up to 3 wt.%, but decreases if
the Cr content is increased to 10 wt.%. When the Cr content is small the Cr is
incorporated substitutionally into the NiO film, and increases Ni++ diffusion by raising
the vacancy concentration. A higher chromium content produces a mixed oxide, and,
eventually, a Cr2O3 protective layer, which significantly decreases the rate of oxidation.
Protective coatings
While one can increase oxidation resistance by alloying, there are limits to how
effectively this can be done, and there are often associated disadvantages, since the alloy
additions affect other properties as well. For this reason structural alloys that are
intended for use in extreme environments are often processed to optimize their
mechanical properties, and then coated with a second alloy that has exceptional oxidation
resistance.
An effective coating must satisfy at least two criteria. It must form a stable
protective oxide film, and it must remain attached to the metal during service, which
often includes repeated cycles to elevated temperature. The first criterion suggests the
use of elements like Cr and Al that are known to form coherent oxides with low
diffusivity. The second criterion requires that the coating remain well bonded to the
substrate through severe thermal cycles. To accomplish this, the coating and its
protective oxide layer must have thermal expansion coefficients that do not differ greatly
from one another or from that of the protected metal. Otherwise the coating will develop
thermal stresses that cause it to spall off of the underlying metal.
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The most successful of the coatings now in use are alloys of cobalt, chromium,
aluminum and yttrium (called CoCrAlY coatings). Cr and Al are the oxidizing species
that form the protective film. Their concentration is balanced with that of Co to minimize
the thermal expansion mismatch with the underlying metal. A small addition of yttrium
substantially improves the retention of the protective layer during thermal cycling. There
are several possible explanation for the yttrium effect. One that has attracted recent
attention is the apparent action of Y in "pegging" the oxide to the coating; Y2O3 forms at
the coating-oxide interface in the form of spikes that penetrate into the coating and act as
pegs to prevent its decohesion during thermal cycling.
12.4 ELECTROCHEMICAL REACTIONS

Most metals are protected from oxidation at room temperature by the slow
kinetics of the process. If this were not true much of engineering, and a good part of
civilization, would not exist. Unfortunately, there is an alternative reaction mechanism
that can oxidize metal at an appreciable rate at ambient temperature. It is a familiar fact
that iron rusts. It converts to its oxide at a disturbingly rapid rate if it immersed in water,
embedded in the soil, or simply left out in the rain and fog. The corrosion of iron and
other structural metals is a costly engineering problem.
The mechanism that permits oxidation at ambient temperature is the
electrochemical reaction that dissolves metal in ionic solution. While most metals ionize
rather easily when they are in contact with an aqueous solution at ambient temperature,
the reaction is impeded by the fact that the release of a positive ion leaves electrons
behind in the metal. The accumulation of negative charge quickly stops the release of
positive ions. If, however, the metal is joined with another in an electrical circuit through
which electrons can flow, the metal can be kept electrically neutral as it ionizes so that
dissolution proceeds at a significant rate. Two metals that are joined electrically so that
electrons can pass between them, and are in contact with an ionic solution through which
ions can migrate to complete an electrical circuit are said to form an electrochemical cell.
One of the metals, the anode in the cell, gradually dissolves. The ions that are released
into the solution as it dissolves ordinarily combine with hydroxyl ions from the water to
form oxide; the net effect is the oxidation of the metal.
The electrochemical reactions that cause corrosion are harmful. However, other
electrochemical reactions are useful, and are used in many important engineering devices.
A familiar example is a battery, in which an electrochemical reaction generates electric
power.
A second important example is electroplating, in which a controlled
electrochemical reaction is used to deposit one metal as a coating on the surface of
another.
In this section we shall first discuss the general principles that govern the
behavior of electrochemical, or galvanic, cells, and then focus on the important issue of
aqueous corrosion and its prevention. Here we will consider only metal removal by
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corrosion. As we shall see later, corrosion can also affect the mechanical properties of a
material through such mechanisms as stress corrosion cracking, corrosion fatigue, and
hydrogen embrittlement.
12.4.1 The galvanic cell
Suppose we place plates of two dissimilar metals, say Zn and Cu, in an solution in
a configuration like that shown in Fig. 12.14. Each metal is in equilibrium with an ionic
solution (electrolyte) that contains its own ion, Zn++ in the case of Zn, Cu++ in the case
of Cu. For simplicity, let both of the solutions be sulfate: ZnSO4 and CuSO4, and assume
that the ion concentrations in the solutions, [Cu++] and [Zn++] are fixed at the same
values (this can be done by setting the concentration of the solution and making it large
compared to the metal). The two metals are in equilibrium with their respective
solutions; nothing further happens.
Now suppose that we change the experiment in two ways. We connect the Zn and
Cu plates with a thin conducting wire, and we connect the solutions with a salt bridge,
which may be just a permeable membrane through which ions such as SO4= can flow to
preserve charge neutrality. This simple act triggers a spontaneous chemical reaction.
The Zn plate begins to dissolve, while the Cu plate grows by the addition of Cu from the
solution. This experiment illustrates two important processes: the galvanic corrosion of
one metal (Zn) by another (Cu) and the electroplating of a metal (Cu) onto the surface of
an electrode. The experimental arrangement in which this happens is called a galvanic
cell.
++
Zn
SO4
Cu
Cu
Zn
SO4
++
+
Zn Zn + 2e - Cu + e - Cu
...
Fig. 12.14: A galvanic cell between Cu and Zn, connected by a sulfate
solution and a wire and voltmeter. The anode (Zn) and cathode (Cu) reactions are indicated.
A galvanic cell is formed because the two metals differ in their electrical potential
(). The ionization reaction at the Zn-solution interface,
Zn Zn++ + 2e-
12.18
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produces an electrical potential within the Zn, Zn, whose magnitude is given by the
Nernst equation
RT
0
Zn = Zn + 2F ln[Zn++]
12.19
where Zn is the standard potential for the half-cell reaction given in eq. 12.18, F is the
Faraday constant , the charge in a mole of electrons,
F = N0e
12.20
where N0 is Avogadro's number and e is the magnitude of the electron charge, the factor
2 appears because there are two electrons produced in the reaction, and [Zn++] is the
concentration of Zn++ ions in the solution. The electrical potential in the Cu is fixed by
the ionization reaction at the Cu interface,
Cu Cu++ + 2e-
12.21
RT
0
Cu = Cu + 2F ln[Cu++]
12.22
and is
When the two metals are joined electrically their potential difference is
[Zn++]
RT
= Zn - Cu = 0 + 2F ln
[Cu++]
12.23
Since the initial concentrations in the two solutions are the same, the potential difference
is
0
= 0 = Zn - Cu
12.24
where 0 is the standard potential for a Zn/Cu galvanic couple through a sulfate
solution. This is the potential that would be measured by a voltmeter placed as shown in
Fig. 12.14.
0
The standard potential, 0, is negative for this particular case; Cu > Zn .

Since electrons spontaneously flow from regions of low potential to regions of high
potential, there is a net flux of electrons from Zn to Cu. The electrons are produced by
the ionization of Zn at the Zn-solution interface according to eq. 12.18, and are consumed
by the formation of Cu from Cu++ ions at the Cu-solution interface by reversing eq.
12.21. The circuit is completed by the flow of SO4= ions toward the Zn across the
membrane separating the solutions. The net reaction is
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Zn + Cu++ Cu + Zn++
12.25
The Zn electrode, where ions and electrons are produced, is called the anode of the cell.
The Cu electrode, where ions and electrons combine to form neutral atoms, is called the
cathode of the cell. In this cell, Zn is corroded by Cu; the Zn anode gradually disappears.
Cu is electroplated by Zn; the Cu anode grows through the deposition of Cu.
The example discussed above uses the metals Zn and Cu. A similar galvanic cell
is established if any two metals are brought into electrical contact with one another while
placed in an electrolyte. Let one electrode be formed of metal, A, which ionizes to an ion
of valence, a, while the other is made of metal, B, which ionizes to an ion of valence, b.
Assume that A is the anode. The two electrode reactions are
A A+a + ae12.26
B
B+b
be-
The half-cell potentials are

RT
0
A = A + aF ln[A+a]
12.27
B =
0
B
RT
+ bF ln[B+b]
When the two electrodes are joined the overall reaction is, per mole of A consumed,
a
a
A + b B+b A+a + b B
12.28
and the potential is

=
RT
[A+a]
+ aF ln +b a/b
[B ]
12.29
where
a 0
0
0 = A - b B
12.30
12.4.2 The electromotive series and the galvanic series

If we ignore the influence of the ion concentration, the identity of the anode and
cathode and the basic cell potential are determined by the standard potential, 0. The
standard potential is the difference between the standard half-cell potentials, 0, of the
anode and cathode. The value of the standard half-cell potential is affected by the nature
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of the solution. As we shall discuss in more detail below, the standard potential
decreases if the solution contains species that interact favorably with the metal ion and
decrease its chemical potential. The half-cell potential is also affected by the
temperature. Hence any tabulation of half-cell potentials is specific to a particular
solution and temperature.
A table of half-cell potentials is, nonetheless, useful. It helps to identify which
electrode will be the anode and which the cathode in solutions like those for which the
tabulation is made, and suggests the magnitude of the galvanic potential when the
concentrations are uniform.
Two tabulations of standard half-cell potentials are ordinarily included in standard
texts on electrochemistry and corrosion. The first is the electromotive force series
(EMF), which is a tabulation of the standard half-cell potentials for the solution of metals
in aqueous solutions of their own simple salts at 25C. Since the zero of potential is
arbitrary, the potentials are given relative to that of the formation of H2,
H+ + e- H2
12.31
whose standard potential is arbitrarily set equal to zero. The electromotive force series
for a number of important reactions is given in Table 1. The reactions are listed in
descending order of 0. It follows that when a galvanic cell includes two reactions in the
series, then, in the absence of concentration effects, the one that appears higher in the
series is the cathode reaction while the one that appears lower is the anode reaction. That
is, the metal that appears higher in the series will corrode that which is listed lower down.
The standard potential of the cell is the difference between the two half-cell potentials.
Table 12.1: The Electromotive Force Series (EMF)
Electrode Reaction
(25C)
Au Au+3 + 3eHg Hg++ + 2eAg Ag+ + eCu Cu+ + eH2 2H+ + 2ePb Pb++ + 2eSn Sn++ + 2eNi Ni++ + 2eCd Cd++ + 2eFe Fe++ + 2eCr Cr+3 + 3eZn Zn++ + 2eMn Mn++ + 2e-
1.50 volts
0.854
0.800
0.521
0.00
-0.126
-0.136
-0.250
-0.403
-0.440
-0.74
-0.763
-1.18
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Zr Zr+4 + 4eTi Ti++ + 2eAl Al+3 + 3eMg Mg++ + 2eCa Ca++ + 2eLi Li+ + e-
-1.53
-1.63
-1.66
-2.37
-2.87
-3.05
Table 12.2: The Galvanic Series in Sea Water

Increasingly anodic
Magnesium
Magnesium alloys
Zinc
Aluminum
Al-Cu alloys
Mild steel
Wrought iron
Cast iron
18Cr-8Ni stainless steel (non-passivated)
50Pb-50Sn solder
Lead
Tin
Nickel
Brasses (Cu-Zn)
Copper
Bronzes (Cu-Sn)
Silver solders
Nickel (passive)
Monel (70Ni-30Cu)
Titanium
18Cr-8Ni stainless steel (passive)
Gold
Increasing cathodic
The second tabulation that is widely given is the galvanic series in sea water,
which is reproduced as Table 2. This tabulation is qualitative. It is simply a columnar
listing of metals in decreasing order of potential. In the absence of concentration effects,
the metal that appears higher in table is cathodic with respect to one that listed lower in a
galvanic couple in sea water. The more cathodic metal will ordinarily corrode the more
anodic one when they are joined in a galvanic couple. The galvanic series incorporates
two changes from the electromotive force series. The solution is different, and the series
lists engineering alloys as well as pure metals. Since engineering alloys are
multicomponent and, often, multiphase materials with complex microstructures, their
standard potentials cover a range of values. The galvanic series indicates the relative
position of this range of values with respect to the standard potentials of other metals and
alloys.
12.4.3 The influence of concentration: concentration cells
The potential of the galvanic cell shown in Fig. 12.14 depends on the concentrations of Zn++ and Cu++ ions as well as on the standard potential for the cell. The governing relation is given by the Nernst equation, eq. 12.23. A decrease in the Cu++ concentration relative to that of Zn++ reduces the potential difference between the two electrodes
and lowers the driving force for the electrochemical reaction. It is even possible, in
theory, to reverse the polarity of the cell, that is, to make the Cu electrode the anode in
the cell by adjusting the ion concentrations.
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low
++
Zn
=
high
++
Zn
Zn
Zn
SO4
SO4
++
++
Zn Zn + 2e - Zn + 2e - Zn
Fig. 12.15: An example of a concentration cell between Zn++ solutions

of different concentrations. The low-Zn++ solution is the
anode; the high-Zn++ solution is the cathode.
The influence of concentration is most obvious in a type of galvanic cell known as
the concentration cell, an example of which is shown in Fig. 12.15. Let both electrodes
be made of Zn, but let the concentrations of the two solutions be [Zn++]1 and [Zn++]2.
Let the two electrodes be connected by a wire and the two solutions by a salt bridge that
neutralizes the solution by passing negative ions. According to eq. 12.23 the potential
difference in this case is
[Zn++]1
RT
= 2F ln ++
[Zn ]2
12.32
which is negative if [Zn++]1 < [Zn++]2. It follows that the electrode that is in contact
with the solution of lower concentration is the anode. It will be corroded, while the
electrode at the cathode grows by adding Zn from the solution.
The behavior of concentration cells simply illustrates how electrochemical
reactions lead to thermodynamic equilibrium. The equilibrium condition of the solution
in Fig. 12.15 is one in which the Zn++ concentration is uniform throughout. This
equilibrium cannot be achieved by Zn++ diffusion through the solution, since the
membrane that separates the two solutions is (by assumption) impermeable to Zn++.
However, it can be achieved by an electrochemical reaction that adds Zn++ ions to the
solution at the anode, where the concentration is relatively low, and removes them at the
cathode, where the concentration is relatively high.
12.4.4 Reactions at the cathode
In addition to Cu++ ions, the solution near the Cu cathode in Fig. 12.14 contains
H+ and OH- ions from the ionization of water. Ordinarily, the solution also contains dissolved O2 gas that has diffused in from the atmosphere. The equilibrium of H+, OH-, and
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O2 leads to two common reactions that compete with electrodeposition to consume electrons at the cathode: the evolution of hydrogen is governed by the reaction
H2 2H+ + 2e-
12.33
while the consumption of oxygen is governed by the reaction

1
1
OH- 4 O2 + 2 H20 + e-
12.34
The half-cell potential for the ionization of hydrogen gas is

H2 =
0
H2
+ 2
RT
[H ]
+ 2F ln [H ]
2
12.35
Equation 12.35 can be written in a form that is easier to use. By convention, for aqueous
solutions at ambient temperature,
0
H2 = 0
12.36
The zero of energy, and, hence, the zero of potential is arbitrary, and electrochemists
have agreed to set the zero so that equation 12.36 holds. The concentration of hydrogen
gas in solution is approximately equal to the partial pressure of hydrogen in the gas above
the solution, in atmospheres pressure. Hence
RT
RT
H2 = F ln[H+] - 2F ln(PH2 )
12.37
The concentration of hydrogen ion in solution, [H+], defines the pH of the solution by the
relation
pH = - log[H+] = - 2.303 ln[H+]
12.38
In these equations H2 is the potential to which an electron is effectively raised when it

joins with H+ to form H2, and is, hence, the effective cathode potential when hydrogen
evolution is the governing reaction at the cathode.
The half-cell potential for the consumption of oxygen in a basic solution is,
OH- =
0
OH-
[O2]1/4
RT
+ F ln
[OH-]
12.39
When the oxygen concentration in solution is determined by equilibrium with a vapor in

which the partial pressure of oxygen is PO2 (measured in atmospheres) , the half-cell
potential is
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OH- =
(P )1/4
RT
O2
+ F ln
[OH-]
0
OH-
12.40
As before, OH- is the potential to which an electron is raised when it joins with
dissolved oxygen and water to produce OH- ions at the cathode.
In most cases the cathode reaction in a galvanic cell is hydrogen evolution or oxygen consumption rather than metal deposition. As we shall discuss further below, the
dominant cathode reaction is the one that leads to the highest cell current. This is usually
the reaction with the greatest half-cell potential, , since this reaction causes the highest
potential difference across the galvanic couple. Unless the solution at the cathode is constrained to have a high concentration of the cathodic metal species, the metal ion
concentration at the cathode is very low, or quickly becomes so by cathodic deposition.
As the metal ion concentration falls to a low value at the cathode, the cathode potential
becomes strongly negative, as shown by eq. 12.27 (the logarithm of a number that is
much less than 1 is large and negative). Hence the cathode reaction ordinarily produces
H2 or OH- rather than deposited metal. In strongly acidic solutions or in solutions that
have low oxygen concentrations, hydrogen is evolved at the cathode. In intermediate to
basic solutions with moderate oxygen concentrations, oxygen is consumed.
The oxygen concentration cell

A galvanic cell that is very important in practice is the cell that is set up by a
significant difference in the oxygen concentration at two electrodes that are otherwise the
same. Consider the cell shown in Fig. 12.16, both of whose electrodes are made of Fe.
Assume that the solutions in contact with these electrodes are approximately neutral (pH
7),. but differ significantly in their oxygen concentrations. According to eq. 12.40, the
solution with the higher oxygen concentration provides the higher electrode potential, so
the electrode that is embedded in this solution should be the cathode of a concentration
cell. The anode is the electrode in the solution that is relatively poor in oxygen.
V
++
Fe Fe + 2e -
Fe
anode:
high
O2
Fe
low
O2
++
Fe
(OH)
cathode:
O2 + 2H2O + 2e- 4 (OH)
...
Fig. 12.16: An oxygen concentration cell between two Fe electrodes.
Fe++ is produced at the low-O2 anode, (OH)- at the high-O2
cathode.
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If we consider only the oxygen solution then the reaction at the anode would
appear to be the evolution of oxygen by the reaction of OH- ions, according to eq. 12.34.
However, there is ordinarily a much more favorable anodic reaction; the electrode
potential for the ionization of iron
Fe Fe++ + 2e-
12.41
is much lower than that for the evolution of oxygen. It follows that Fe++ ions are
produced at the anode, and the overall reaction is
1
Fe + 2 O2 + H2O Fe++ + 2OH-
12.42
Equation 12.42 is the reaction that usually governs the atmospheric corrosion of iron.
The Fe++ ions and the (OH)- ions react to form iron oxide (rust). This simple example
shows how a gradient in the concentration of oxygen can cause corrosion even in the
absence of dissimilar metal contact.
12.4.5 The influence of an impressed voltage
Since the galvanic cell is an electrical circuit, it is possible to impose a voltage to
control the direction or rate of the reaction. External voltages are commonly used for
three purposes. First, an impressed voltage can halt the corrosion of a natural anode by
reversing the galvanic cell. If the natural potential of the cell is , a battery that imposes
an opposite potential that is greater than reverses the anode and cathode, and stops
corrosion of the anode. This is one to accomplish the cathodic protection of iron, a
method of corrosion prevention that we shall discuss further below. Second, an
impressed voltage can be used to electroplate a metal coating onto a metal that is
naturally anodic to it. For example, gold coatings are sometimes electroplated onto metal
surfaces to beautify them or protect them from corrosion. Since Au is cathodic to all
metals, it is ordinarily impossible to design a natural galvanic cell that will accomplish
this. However, an impressed voltage can be used to reverse the cell and electroplate Au
onto almost any metal. Third the rate of corrosion of the anode is governed by the cell
potential. Using an external potential, it is possible to control the voltage to a value that
sets the rate of corrosion. This technique provides a method of corrosion protection in
that it can be used to minimize the corrosion rate. It is also used in electroplating, to
control the rate of metal deposition on the cathode.
12.4.6 Thermodynamics of the galvanic cell
In discussing the galvanic cell, we have taken the standard half-cell potentials as
experimental fact. To understand how these potentials arise, and why they have the
values they do, it is necessary to consider the thermodynamics of the galvanic cell more
closely. There are three species that appear in a standard half-cell reaction that governs
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the ionization of a metal: the atoms in the metal, the ions that go into solution, and the
excess electrons that are left behind in the metal. Let the reaction have the generic form
M M+ + e-
12.42
The change in Gibbs free energy per mole of metal consumed is

g = (M+) + (e-) - (M)
12.43
where (A) is the chemical potential of the species, A. To solve equation 12.43 we need
to know the chemical potentials of each of the species involved.
The work function and the contact potential

First consider the electrons in a metal that is not in contact with an ionic solution.
As we discussed in Chapter 2, the electrons in a metal fill its available energy states up to
the Fermi energy, EF. The chemical potential of a species in a system is defined as the
work done, or energy increment, when an infinitesimal amount of that species is added.
Since the addition of an electron to a metal adds the energy, EF, the chemical potential of
an electron in a neutral metal is equal to EF.
To compare the electron energies in different metals it is necessary to set the zero
level of the energy in a way that guarantees that the energies are measured with respect to
the same reference. This is done by converting the electron energy into a potential
according to the relation
E = - e
12.44
where e is the electron charge, and setting the zero of the potential at the same reference
for every material. The chemical potential per mole of electrons at potential, , is, then,
e- = N0E = - F
12.45
where N0 is Avogadro's number and F is the Faraday constant, the magnitude of the
charge of a mole of electrons.
The Fermi energy of a neutral metal in free space is negative, since the electrons
are bound in the solid, as illustrated in Fig. 12.17. The potential at the Fermi level is
F = - EF/e
12.45
and is positive. The potential, F, is called the work function of the solid, since the work,
eF, must be done to raise the energy of the electron to the level at which it can flow out
of the solid into free space.
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Free space
e F
EF
filled electron states
Fig. 12.17: Schematic diagram of electron energies in a simple metal,

illustrating the Fermi level, the potential increase to the free
space value at the metal surfaces, and the work function.
Now suppose that two different metals, A and B, are joined together by a conducting wire, as shown in Fig. 12.18. The two metals have different Fermi energies, and,
hence, have different internal potentials. Let these be A and B, where B > A. There
is, hence, a potential difference between the two metals of magnitude
= B - A
12.47
This is called the contact potential, since it is developed spontaneously when the two
metals are joined. Since electrons have lower energy in regions of higher potential,
electrons flow through the wire from A to B. The accumulation of electrons (excess
negative charge) in metal B lowers its potential (raises the Fermi energy) while the loss
of electrons (excess positive charge) in metal A raises its potential (lowers the Fermi
energy). A current continues to flow until the potentials in the two metals become the
same. At this point the Fermi level, EF, is the same in both metals, and, hence, the
electron chemical potential is also the same. Equilibrium is established.
EF
eA
e B
e
EF
Fig. 12.18: Energy diagram illustrating the source of the contact

potential when two metals are joined together. Electrons will
flow from A to B until EF has the same value in both metals.
The contact potential is a principle source of the galvanic potential that develops
when the two metals are joined in a galvanic cell, although, as we shall see, the ionic part
of the cell also plays an important role.
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In addition to its importance in galvanic cells, the contact potential between

dissimilar conductors is also responsible for the important junction properties of
semiconducting devices, which we shall discuss in Chapter 14. It is also used in the
temperature measuring device known as a thermocouple. It is worth making a small
digression to describe how a thermocouple works. A thermocouple consists of wires of
two different metals that are joined at one end to establish an electrical contact and are
connected at the other end to a potentiometer that measures the contact potential between
them. Not only are the Fermi energies of the two metals different, but they also have
different thermal derivatives. The contact potential is a function of temperature, that can
be measured once to calibrate the thermocouple. Since the contact potential is
established at the dissimilar metal junction, it measures the temperature at the place
where the junction is located. One can, for example, measure the temperature within a
furnace by placing the junction of the thermocouple wires at the point where the
temperature is to be measured, and reading the temperature from a potentiometer located
well outside the furnace.
The chemical potential of an atom in solution

Now consider the chemical potential of the metal, M, in the reaction given in eq.
12.43. For generality, assume that the metal is a solid solution that contains metal M
along with other species. Let the concentration of M be denoted [M].
The chemical potential of a species, M, in a solid solution can always be written
*
M = M + RT ln(aM)
*
12.48
o
where M is the potential of the species in its pure state (M is a function of T and P,
but we assume these are fixed at ambient values), and aM is the activity of M in its
solution. In fact, eq. 12.48 defines the activity, aM. The activity is a function of the
composition of the solution, but has well-defined values in two limits. First, when M is
the solvent and its concentration is nearly 1, the activity is equal to the concentration:
aM = [M]
([M] 1)
12.49
This relation is one form of Raoult's Law. Second, when M is a solute and its concentration is very small, aM is proportional to the concentration:
aM = M[M]
([M] << 1)
12.50
where M is a constant known as the activity coefficient. In either of these two cases we
can replace eq. 12.48 by the simpler relation
0
M = M + RT ln[M]
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where
0
M = M
([M] 1)
12.52
0
*
M = M
+ RT ln(M)
([M] <<1)
These two limits are sufficient to cover most of the cases we will be interested in, so we
shall assume that eq. 12.51 holds.
The physical reason for the difference between these two expressions lies
ultimately in the environment of an M atom in the solution. When [M] 1 an M atom is
surrounded almost entirely by atoms of its own kind. Since its environment is almost
identical to that it should have in pure M, its chemical potential is almost the same. On
the other hand, when [M] << 1 an M atom is surrounded almost entirely by solvent
atoms. The chemical potential of an isolated atom of M is determined almost entirely by
0
its interaction with the solvent atoms, so M ordinarily has a very different value than it
would have in pure M. The activity coefficient, M, has no fundamental significance; it is
0
simply a number that measures the difference between M in dilute solution and that in
the pure metal. If the interaction between M and the solvent species is energetically
0
*
favorable, M for the dilute solution is less than M , so M < 1. When the interaction
is energetically unfavorable, M > 1.
The chemical potential of an ion in a dilute solution

Now consider the potential of the ion, M+, in a dilute aqueous solution of the sort
we are interested in here. Since the ion is charged, its chemical potential is affected both
by its concentration and by the electrical potential of the solution. The electrical potential
of the solution that contains M+, M+ , must necessarily be considered if the solution
contains an excess of positive or negative ions. The electrical contribution to the
chemical potential of a positive ion of charge, z, in a potential, , is zF, since this is the
electrical work that would have to be done to move a mole of ions to this potential from a
place where the potential was zero. Using equation 12.51, the chemical potential of a
singly charged ion, like M+, is
0
M+ = M+ + FM+ + RT ln[M+]
12.53
where M+ is the reference chemical potential for the dilute solution.
The potential at a metal-solution interface

We can now combine these relations to find the half-cell potential for the reaction
M M+ + e-
12.42
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When equilibrium is established at the interface, g = 0 in eq. 12.43. Hence

M - M+ - e- = 0
12.54
Substituting equations 12.45, 12.51, and 12.53, and letting [M] = 1 for the pure metal, we
have
0
M - M+ - FM+ + FM - RT ln[M+] = 0
12.55
This equation can be solved for the potential difference between the metal and the
solution. The result is
RT
0
M = M - M+ = M + F ln[M+]
12.56
where
0
0
M
M+ - M
12.57
This equation is identical in form to the basic equation (12.27) for the half-cell potential
of an electrode in a galvanic cell. Note, however, that the standard potential (eq. 12.57)
is not quite the same as that which appears in the electromotive series (Table 1). Since
electrochemists measure standard potential relative to that for ionization of hydrogen, the
potential in the electromotive series differs from that in equation 12.56 by a constant,
which subtracts out when two half-cell reactions are combined in a galvanic cell.
It is useful to consider the physical meaning of equation 12.56. This equation describes a situation that leads to a dynamic equilibrium in which the rate of creation of M+
ions and electrons is precisely equal to the rate of their recombination to generate pure M.
Consider four prototypic situations. First, suppose that we place a sheet of M in a neutral
solution that contains no M+ ions. Since, initially, M+ is zero and M is positive, the
left-hand side of the equation is positive, while the right-hand side is negative since [M+]
is arbitrarily small. Therefore, some M ionizes to M+ to establish equilibrium. As it does
so, the right-hand side of the equation shifts toward positive values as [M+] increases.
However, ionization causes the accumulation of excess electrons in the metal and excess
ions in the solution. The excess electrons decrease M, while the excess ions increase
M+ , so the left-hand side of the equation decreases. The two sides of the equation
move toward one another until they become equal and equilibrium is established.
Second, suppose that we place a small sheet of M in a large body of neutral
solution that contains M+. If the solution is very large, [M+] is essentially fixed, and
M+ remains very close to zero. The right-hand side of the equation then has a fixed
value. M is either ionized or plated at the interface until the electron concentration within
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the metal reaches a value such that M is equal to this value. It follows that we can use
equilibrium with an ionic solution to fix the value of the potential within the metal.
Third, suppose that the solvent of the solution is replaced by one that interacts
0
0
strongly and favorably with M+. In this case M+ decreases, so M decreases and more
M+ is produced by ionization. If the solution is so large that [M+] is fixed, electrons
accumulate in the metal until M decreases to its new equilibrium value.
Fourth, suppose that the nature of the metal is changed, for example, by making it
polygranular or deforming it to introduce dislocations or other crystallographic defects.
These microstructural changes raise the chemical potential of the metal in its pure state,
0
0
M . As a consequence, they lower M and make the metal more anodic. This has the
important consequence that one can form a galvanic couple between two samples of the
same metal by processing one of them to introduce defects. The defective sample is the
anode in the galvanic couple, and is corroded by the more perfect one. The opposite
effect is achieved by alloying the metal with solute to form a solution. If the solute is
dilute, then, whatever its nature, the chemical potential is lowered according to eq. 12.51.
It follows that one can form a galvanic couple between a pure metal and a similar metal
that is lightly alloyed. The alloy is the cathode, and corrodes the pure metal.
-
Metal
e M
+
e M
+
e M
+
e M
+
e M
+
e M
Solution
...
Fig. 12.19: The double-layer of charge at the interface between a metal
and an electrolyte. The figure assumes excess electrons in
the metal and excess positive ions in the solution.
Finally, consider where the excess electrons and ions will normally be found.
Since the electrons are negatively charged and the ions are positively charged, the two
species attract one another. The excess electrons and ions form layers of excess charge
along the interface, with the electrons just inside the solid and the ions just inside the
solution, as illustrated in Fig. 12.19. If there is a deficit of charge in the metal, the holes
(missing electrons) are concentrated along the interface of the metal while the excess
negative ions lie along the solution side of the interface. This configuration of parallel
layers of charge is called the double-layer of charge. The double-layer contains
essentially all of the excess charge, and, since the total excess electron charge equals the
total excess ion charge, it acts as a thin capacitor with balanced charge. Excepting the
region within the double-layer, the metal and the solution are electrically neutral; hence
the potential is constant in the interiors of both the metal and the solution. The potential
gradient that changes the value of from M to M+ lies across the double-layer. A
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double-layer of charge is formed at every surface where the potential changes; hence
there is a double-layer at virtually every interface between a metal and an electrolyte.
The galvanic cell

Now assume that M is joined with another metal, P, to form a galvanic cell. For
simplicity, let P also form a monovalent ion
P P+ + e-
12.58
and let M and P be in contact with solutions of their ions that have equal concentrations.
If P is the cathode, the cell reaction is
M + P+ P + M+
12.59
and the potential of the cell is

0
= P - M = P - M = (P - M) - (P+ - M+ )
12.60
12.5 THE KINETICS OF ELECTROCHEMICAL REACTIONS

The engineering significance of an electrochemical reaction is usually determined
by its kinetics, that is, by the rate at which the reaction proceeds. To sustain the reaction
each of the electrons that is liberated at the anode must travel to the cathode and be
consumed there. Since each ion that is liberated at the anode produces a given number of
electrons, the reaction rate is simply proportional to the current that circulates through the
electrochemical cell.
12.5.1 The current in an electrochemical cell
Since the electrochemical cell is a simple electrical circuit, the electrical current,
I, must be the same for every cross-section through the circuit, and must obey Ohm's
Law:
V = IR
12.61
where V is the total voltage drop between the electrodes and R is the total resistance. In
a simple galvanic cell, that is, one that does not contain a battery or other voltage source,
V =
12.62
the galvanic potential between the electrodes. The total resistance, R, is the sum of the
resistance of the metallic circuit through which the electrons pass and the effective
resistance of the ionic solution through which the ions pass. The current that is given by
eq. 12.61 is the electric current. Recall that, by the strange historical convention of
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electrical engineers, the electric current is the flow of positive charge, and is equal and
opposite to the electron flow. While electrons flow from anode to cathode through the
metallic conductor, and negative ions flow from cathode to anode through the solution,
the electric current travels from cathode to anode through metal, and from anode to
cathode through the electrolyte.
You might guess that we could find the current in a simple electrochemical cell by
inserting the value of that is determined by the thermodynamics of the cell according
to eq. 12.60. But this is not the case. The potentials that appear in eq. 12.60 apply when
both electrodes are in equilibrium. When the electrodes are in equilibrium there is no net
ionization and no net production or consumption of electrons. To induce a current we
must perturb the anode and cathode potentials so that equilibrium is violated and the
reactions proceed at a finite rate.
For example, let the anode reaction be
M M+ + e-
12.63
a = M - M+
12.64
and let its potential be
where M is the potential in the metal and M+ is the potential in the solution at the
anode. If
a = a = M
12.65
where a is the equilibrium potential at the anode, then the anode is in equilibrium and
no net reaction happens. To drive the anodic reaction we must increase a so that
electrons are attracted into the metal and ions are attracted into the solution. When this is
done the electrode is said to be polarized. The rate of reaction, and, hence, the current at
the anode, ordinarily increases with the degree of polarization as measured by the
difference, a - a.
Similar reasoning applies to the cathode. If the cathode potential, c, is equal to
its equilibrium value, c, no reaction occurs. To drive the cathodic reaction we must decrease c so that electrons are attracted to the solution. The current at the cathode
ordinarily increases with the potential difference c - c.
In an active galvanic cell both electrodes must be polarized so that both pass current. The electrode potentials and the resulting current are determined by two conditions.
First, the total current is the same at the anode and the cathode:
Ia = Ic = I
12.66
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Second, the potential difference between the anode and the cathode satisfies Ohm's Law,
which, in the absence of an impressed voltage, reads
V = (c - a) = IR
12.67
where R is the sum of the resistances of the metallic and ionic paths. If R is small,
c ~ a =
12.68
where is the potential that leads to the same overall current at the two electrodes. Eq.
12.68 is usually a good approximation in natural corrosion cells where the anode and
cathode are physically close to one another. In this case is called the cell potential, or,
in the specific case of aqueous corrosion, the corrosion potential.
12.5.2 The current-voltage characteristic
To solve the simultaneous equations 12.66 and 12.67 we must know the currentvoltage characteristics for the two electrodes. The current-voltage characteristic of an
electrode relates the current density, j, at the electrode to the overpotential, - . The
current, I, at the electrode is the product of its current density and its area, A:
I = jA
12.69
If the resistance, R, is negligible, the corrosion potential, , is the potential at which

jaAa = jcAc
12.70
where the subscripts a and c refer to the anode and cathode, respectively.
If the current-voltage characteristics of the two electrodes are known, the cell potential and current can be found by simple graphical methods, as illustrated in Fig. 12.20.
Fig. 12.20(a) applies when the electrodes have the same area and the circuit resistance, R,
is negligible. The cell potential, , is determined by the intersection of the two currentvoltage characteristic curves. Fig. 12.20(b) applies when the electrode areas are different.
In the case shown, the anode is much smaller than the cathode. The equality of the
overall current requires that the current density at the anode be higher than that at the
cathode by the factor Ac/Aa (eq. 12.70). As the area ratio becomes larger, the anode
current density increases (the rate of corrosion of the anode increases) and the cell
potential rises toward the equilibrium potential of the cathode. Fig. 12.20(c) applies
when the circuit resistance, R, is appreciable. As illustrated in the figure, the cell
potentials at the anode and cathode are separated by the factor, IR, and the current density
is lower than its value in the absence of the resistance.
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cathode
cathode
A c j c = A aj a
c
= IR
a
anode
anode
ln (j)
ln (j c)
ln (ja)
ln (j)
ln (j)
(a)
(b)
ln (j)
ln (j)
(c)
Fig. 12.20: Graphical solution for the electrode potentials and currents
under three conditions: (a) Ac = Aa, R = 0; (b) Ac >> Aa, R =
0; (c) Ac = Aa, R 0.
To go further we need to understand the current-voltage characteristics of the
anode and the cathode. First consider the anode. The current density at the anode (ja) is
equal to the rate at which positive ions are liberated per unit area of anode, multiplied by
the ionic charge:
dN
ja = zF dt
12.71
where z is the charge per ion, zF is the charge per mole of ions, and dN/dt is the mole
number of ions produced per unit area per unit time. The reaction at the anode occurs in
two sequential steps. First, positive ions are produced at the anode and liberated into the
solution. Once in the solution they migrate toward the cathode. The rate of ion
production is determined by the slower of these two processes. If the ionization reaction
is slower, the current is said to be activation controlled. If ion migration away from the
interface is slower, the reaction is mass transport controlled. However, mass transport
control at the anode almost invariably leads to an even more restrictive reaction. If ions
accumulate at the cathode, they tend to react to form oxide or hydroxide films. If these
are insoluble, they coat the interface, severely restricting the reaction rate. In this case
the anode is said to be passivated.
The reaction steps that occur at the cathode are similar, with the difference that
the cathode reaction may either consume positive ions, as in the case of metal deposition
and hydrogen evolution, or consume oxygen to produce negative ions. In either case the
reaction involves an ionization step that consumes or produces ions, and a diffusion step
that delivers the reacting species to the surface. Hence the cathode reaction may be
activation controlled or mass transport controlled. Passivation does not normally occur at
the cathode.
The three possible rate-limiting steps, activation, mass transport, and passivation,
lead to different reaction kinetics.
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Activation control
When the current is low it is invariably controlled by the rate of ionization, since
there is ample time for the ions to migrate away from the interface. Ionization is a
thermally activated process, whose rate is ordinarily given by an equation of the form
g
dN
=
Aexp
2RT
dt
12.72
where A is a constant, g is the free energy change per mole of ions, and the factor 2 appears in the exponent because both ions and electrons are produced in the reaction. The
free energy change, g, for ionization at an electrode is related to the electrode potential
according to
g = zF( - )
12.73
where the (+) sign applies at the anode (positive ions produced) and the (-) sign applies at
the cathode (positive ions consumed or negative ions produced). Combining equations
12.71, 12.72 and 12.73, the current-voltage characteristic at the anode can be written in
the form
ja
(a - a) = ka lnj
a
12.74
where ka and ja are constants. (This equation applies when a is significantly greater
than a. When a a we must also consider the reverse reaction that creates neutral
atoms from ions. When a = a the forward and reverse reactions happen at the same
rate, and the net current is zero.)
When the cathode is activation-controlled, a similar analysis shows that its
current-voltage characteristic is given by
jc
(c - c) = kc lnj
c
12.75
where kc and jc are constants.

The cell potential, , under activation-controlled conditions are determined as
shown graphically in Fig. 12.20. In the example used in Fig. 12.20 it is assumed that k
and j have comparable values at the two electrodes. This is not necessarily the case.
The constant, k, is inversely proportional the ion charge, and the constant, j, is
proportional to the logarithm of the rate constant, A. The intersection of the two curves,
which determines the cell potential, , always falls between the equilibrium potentials,
c and a. However, may lie anywhere in this range.
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Finally, consider the case in which two or more independent reactions can occur
at an electrode. The most common case is the competition between metal deposition,
hydrogen evolution, and oxygen consumption at the cathode. The dominant cathode
reaction is the one that produces the highest cell current. This is ordinarily the reaction
that has the largest equilibrium cathode potential, c. However, exceptions are possible.
If a cathode reaction has a smaller value of , but has a smaller value of k or a larger
value of j, it may produce a higher cell current. An example is given in Fig. 12.21.
cathode
anode
ln (j)
...
Fig. 12.21: Graphical illustration of a case in which a cathodic reaction
with a relatively low equilibrium potential, , can lead to a
higher cell current (j), and, hence, a higher reaction rate.
Mass transport control

Mass transport may control either the anode or cathode current. It is most often
encountered as the limiting factor in the cathode current when the cathode reaction
consumes oxygen. If the oxygen content is relatively low, the rate of oxygen
consumption by ionization at the cathode may exceed the rate at which oxygen can be
delivered to the cathode so that the current is limited by the rate of oxygen diffusion to
the surface.
cathode
solution
cO
...
Fig. 12.22: Mass transport control due to oxygen starvation at the
cathode.
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The maximum current that can be produced by oxygen consumption at the

cathode is equal to the rate at which oxygen can be delivered to the cathode by diffusion
from the solution. We can estimate this current from the following simple argument. Let
the concentration of oxygen molecules (O2) in the solution be cO, let the oxygen
concentration at the electrode surface be zero (all oxygen is consumed), and approximate
the oxygen profile by assuming that c increases linearly to cO over an effective diffusion
distance, , as shown in Fig. 12.22. The flux of oxygen to the interface is, then,
dc
DcO
J = - Ddx =
12.78
where D is the diffusivity of oxygen molecules in the solution. The oxygen consumption
reaction at the cathode can be written
O2 + 2H2O + 4e- = 4(OH)-
12.79
Hence each oxygen molecule produces four negative charges, so the maximum possible
current density is
(jc)max = 4FJ =
4FDcO
12.80
When the cathode potential is such that the cathode current is much less than this value,
the current is determined by the ionization rate (eq. 12.77). However, as the current approaches the limiting value given by eq. 12.80 the current-voltage curve drops to an
asymptote at (jc)max, as diagrammed in Fig. 12.23. The cell current cannot exceed
(jc)max, and reaches this value if the current characteristic of the anode does not intersect
that of the cathode at j < (jc)max, as illustrated in Fig. 12.23.
cathode
anode
ln ( jmax )
ln (j)
...
Fig. 12.23: Decrease of cell current and potential due to mass transport
control at the cathode.
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In a large, quiescent solution the diffusion distance, , is proportional to the mean

diffusion distance, 2Dt , and, hence, increases with time. It follows that (jc)max
decreases with time. The cell current is eventually controlled by mass transport, and
decreases with time. However, real solutions are almost always stirred by convective
currents or by fluid flow. As the flow rate increases, decreases. The limiting current
(jc)max increases with the flow rate, and the cell current returns to the activationcontrolled value when the flow rate is very high.
This effect is responsible for the fact that the rate of corrosion of a metal in
flowing water is often much higher than the rate in still water, and increases with the flow
rate.
Passivation
When mass transport begins to limit the reaction at the anode, metal ions
accumulate there. If the metal is one that can form a coherent oxide or hydroxide at the
interface by reacting with the solution, then a film forms and seals the anode. The film
drives the cell current to a very low value since ions must diffuse through the film to
reach the solution. This phenomenon is called passivation.
+3
Al2 O3
Al
soluble oxides
The passivating film forms when the ion concentration at the anode exceeds a
critical value. In the unpassivated condition, the ion concentration is determined by a
balance between the rate at which ions are produced by ionization and the rate at which
they migrate into the solution. It follows that the ion concentration increases with the
anode potential, a, and that passivation occurs when the anode potential reaches a
critical value, called the passivation potential, p, which depends on the nature of the
anode and the composition of the electrolyte.
Al
pH
Fig. 12.24: Simplified form of the Pourbaix diagram for aluminum. The
passivating oxide, Al2O3, is stable at intermediate values of
the pH.
Assuming that the electrolyte is an aqueous solution, its most important
characteristic is its acidity, as measured by its pH. Oxide films are formed when metal
ions react with (OH)- ions. For a given concentration of metal ions, oxides only form if
the (OH)- concentration, and, hence, the pH, exceeds a critical value. Moreover, most
metals can form any one of several oxides or hydroxides, and the nature of the film that is
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formed also depends on the pH. Since the type of oxide is determined by the metal ion
concentration and the pH, and since the metal ion concentration is determined by the
anode potential, it is possible to construct a type of "phase diagram" that identifies the
presence and type of oxide as a function of the pH and the anode potential, a. Such a
diagram is called a Pourbaix diagram after its inventor. A simple example is given in
Fig. 12.24.
The passivation potential can be estimated from the Pourbaix diagram of the
anode. If the pH of the solution is such that a stable oxide forms, the passivation
potential is given approximately by the lowest potential at which it appears in the
Pourbaix diagram. If the pH is such that no stable oxide forms, the anode does not
passivate. However, a Pourbaix diagram must be used with some caution. Not all oxides
make coherent films; some are soluble or form loose, porous aggregates. Even those
oxides that do form coherent films do not necessarily do so at the lowest potential at
which they are stable.
transpassive
cathode1
passive
p
cathode 2
active
anode
ln (j)
Fig. 12.25: Current-voltage characteristic for a metal that passivates at
intermediate potential. Current-voltage characteristics are
drawn for two cathodes. Note that the cathode that has the
lower produces the higher cell current.
When a metal does passivate its current-voltage characteristic takes the rather
strange form shown in Fig. 12.25. The current increases logarithmically with the
potential until the passivation potential is reached. It then decreases dramatically, and
remains very small until the potential becomes so high that new anodic reactions, such as
the decomposition of water to oxygen and hydrogen ions, intrude and attack the oxide
film.
The effect of passivation on the cell current is illustrated in Fig. 12.25.
Surprisingly, a metal that passivates is corroded by a cathode that has a relatively small
equilibrium potential, since the current-voltage characteristics intersect below the
passivation potential, but is not significantly corroded by a cathode with a relatively high
equilibrium potential, since the current-voltage characteristics intersect at > p.
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12.6 AQUEOUS CORROSION IN ENGINEERING SYSTEMS

Engineering systems are most often corroded by aqueous solutions that are common in the environment. Common problems include atmospheric corrosion by water vapor, rain or salt-water spray, corrosion by immersion in fresh or salt water, and corrosion
by ground water in the soil.
Aqueous corrosion only happens when the corroded metal is an integral piece of a
complete galvanic cell. This requires that the two materials that act as anode and cathode
are in both electrical contact through a conductor and ionic contact through an electrolyte.
Aqueous corrosion is only an engineering problem if the rate of corrosion leads to
significant damage or failure in a time less than the expected lifetime of the device.
Since the rate of corrosion is determined by the current density at the anode, corrosion is
only a problem if the current density is reasonably high.
Where aqueous corrosion is a potential problem, it can be addressed by using
corrosion protection schemes. These employ one of two basic tactics. The first is to
break the electrical circuit or alter it so that the rate of corrosion is negligible. The
second is to provide an alternate circuit so that corrosion occurs in unimportant places
within the engineering system.
12.6.1 Corrosion cells in engineering systems
The three most common sources of galvanic cells in engineering systems are dissimilar metal contact, microstructural surface couples, and oxygen concentration cells.
Dissimilar metal contact

Whenever two different conductors (metals or semiconductors) are brought into
electrical contact in the presence of an ionic solution a galvanic cell develops. The anode
in the cell is corroded unless some protective mechanism intrudes. Dissimilar metal
contact usually establishes a high potential difference, and often causes rapid corrosion,
particularly if the anode in the cell has a much smaller surface area than the cathode.
Most of the spectacular corrosion failures that color the history of engineering have this
cause.
One can identify the cathode in the cell that is formed by contact between metals
A and B by finding the sign of the potential for the reaction
a
a
A + b B+b A+a + b B
12.79
The potential is given by eq. 12.29. If the potential is negative, A is the anode and the
reaction proceeds in the direction of the arrow. However, the reaction at the cathode is
ordinarily not the condensation of B, but the hydrogen evolution or oxygen consumption
reactions discussed in Section 12.4. The dominant reaction at the cathode is the one that
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yields the highest current which is, ordinarily, the one that provides the highest potential
difference.
The implications of dissimilar metal cells for engineering design is straightforward. Whenever two different conductors are used in proximity to one another, rapid
corrosion is a possibility that must be taken seriously. Dissimilar metal couples are likely
to be found in bolted or riveted structures, where the bolts or rivets are often made of a
very different alloy than the structural metal, in piping systems, where different metals
are used for various sections of pipe (for example, municipal water systems usually use
steel pipe while individual homes use copper pipe), and in microelectronic devices, where
many different conductors are used in intimate contact with one another.
Microstructural couples
Galvanic couples are also formed when nominally uniform metals are brought
into contact with an electrolyte. The reason is that the metal surface is never perfectly
uniform. Nonuniformities produce galvanic cells in which local areas that have relatively
high free energy act as anodes while those that have relatively low free energy behave as
cathodes. For this reason, grain boundaries are anodic to grain interiors, deformed (and,
hence, defective) regions are anodic to those that are less heavily deformed, and regions
that are relatively low in solute are normally anodic to those that are higher.
When a metal, A, is in contact with a uniform electrolyte, two different areas of
its surface, A1 and A2, may react according to the relation
A1 + A+a A2 + A+a
12.80
The anode can be identified by comparing the free energies of A1 and A2; the region with
the higher free energy density is the anode. Again, however, the cathode reaction in the
actual cell is usually not the deposition of metal, but the evolution of hydrogen or consumption of oxygen, whichever provides the higher potential.
The corrosion of a nominally homogeneous metal that is placed in a homogeneous
electrolyte is often relatively slow and uniform over the surface. The reason is that the
locally active regions of the surface corrode away. Other regions become active, and the
site of corrosion gradually shifts over the surface. This uniform corrosion may not be
very important unless the metal part is intended for long-time service, as, for example, a
steel beam in a building, or unless the environment is particularly severe, as in the
corrosion of unprotected automobile bodies on the salted roads of the Northeastern
United States.
When the metal is inhomogeneous on a macroscopic scale its corrosion may be
more serious. Macroscopic heterogeneities are often introduced during processing. For
example, the weld in a welded plate differs in microstructure and, often, in composition
form the plate itself, and the small radius or corner of a severely formed metal part has a
different microstructure from the relatively undeformed areas of the part. These largePage 428
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scale inhomogeneities produce permanent galvanic couples that concentrate corrosion in

particular places on the part.
Oxygen concentration cells

The final common source of galvanic couples is the oxygen concentration cell that
was discussed in Section 12.4. As shown by eq. 12.40, the cathode in an oxygen concentration cell is located where the solution that contacts the metal is relatively rich in
oxygen; the anode is located where the solution is relatively poor. However, if the metal
is one that is susceptible to corrosion, the reaction that occurs at the anode is metallic
corrosion, since this provides a higher potential, and the overall reaction is
a
a
A + 4 O2 + 2 H2O A+a + aOH-
12.81
The metal, A, is corroded at the cathode.

Oxygen concentration cells may be produced by either the electrolyte or the
metal.
The electrolyte creates an oxygen concentration cell when it has an
inhomogeneous oxygen concentration. The usual reason is oxygen enrichment at the
water-vapor interface, where oxygen enters from the atmosphere. A simple example is a
drop of water on a metal surface. Oxygen enters the drop along its periphery. Hence the
solution near the periphery is cathodic with respect to the solution in the interior of the
drop, and the metal inside the drop is corroded. A second example is when a metal is
partly immersed in water, a situation that applies to bridge pilings and ship hulls, among
many other engineering structures. The layer of water very near the surface is oxygenrich because of its contact with the atmosphere. The metal-water interface just beneath
the water line is, therefore, cathodic to the interface below it. Corrosion occurs
predominantly near, but just beneath the water line, where the gradient in the oxygen
concentration is greatest.
The metal produces an oxygen concentration cell when it contains pits or
crevices. When the metal is exposed to electrolyte, the oxygen inside the crevice is partly
consumed by local corrosion. The oxygen cannot be replenished nearly as quickly as that
on the free surface because of the tortuous diffusion path that must be followed to access
the bottom of the crevice. Hence an oxygen concentration cell is established between the
bottom of the crevice and the surface of the metal outside the crevice. This tends to
deepen the crevice, driving it into the material.
Pitting or crevice corrosion is a damaging form of attack because it is localized. It
is a particularly serious problem in thin-walled structures, such as tank walls and automobile fenders, since it can lead to rapid perforation of the wall. Crevice corrosion happens
almost whenever crevices are present on a surface. Common sites are at bolts and rivets,
and at places where metal plates are joined so that they overlap one another. Pitting
corrosion develops spontaneously when corrosion is localized to initiate a pit. Pitting is
particularly likely when a painted or coated layer is locally broken. Pitting also occurs on
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Fall, 2008
bare metal surfaces. In this case it is initiated by rapid corrosion at local anodes. Rapid,
local corrosion ordinarily requires a relatively high corrosion potential that is sustained
for some reasonable period of time. Corrosion engineers define a "pitting potential" that
is required to initiate pitting on a bare surface. To develop the pitting potential there
must be strong local couples, such as those produces by dissimilar metal contact,
weldments, or deformation gradients at bends or corners. Once pitting has initiated, it is
usually self-sustaining and eventually causes perforation of the metal.
12.6.2 The corrosion rate
The rate of aqueous corrosion is governed by the kinetic relations developed in
Section 12.5. The local rate of corrosion at the anode is proportional to the current
density at the anode, which is related to the current density at the cathode by eq. 12.68.
The corrosion potential, a, is determined by the current-voltage characteristics of the
anode and cathode and the resistance of the cell according to eq. 12.75. The currentvoltage characteristics of the anode and cathode are determined by the rate-limiting steps
in the ionization reactions at the two electrodes as described in Section 12.5.2. In
practice, the corrosion rate usually increases with the equilibrium potential difference, c
- a, and with the area ratio, Ac/Aa, unless passivation occurs at the anode or mass
transport rules at the cathode. The kinetic features that are important in engineering
design include the following.
The increase in corrosion rate with the equilibrium potential difference has the
consequence that high corrosion rates must be expected when there is dissimilar metal
contact, a substantial difference in oxygen concentration, or a significant change in the
composition or microstructure of the material. Hence the corrosion engineer is anxious to
avoid dissimilar metal cells, crevice corrosion, or microstructural cells that develop at
weldments or regions of high local deformation in formed parts.
The increase in corrosion rate with the area ratio, Ac/Aa, has the consequence that
one must particularly avoid situations in which a small anode is in ionic contact with a
large cathodic area. For this reason, bolts, rivets and other fasteners should, if possible,
be cathodic to the metal they fasten and crevices should be avoided. If a metal surface is
protected with a cathodic coating, such as a gold coating, one must be very careful to
avoid breaks in the coating since these may lead to intense corrosion. Even passivation
may not protect a small anode against corrosion by dissimilar metal contact. The
corrosion potential increases with the area ratio, and may reach trans-passive values if the
equilibrium potentials are sufficiently different.
The rate of aqueous corrosion in non-acidic solutions is often limited by oxygen
diffusion at the cathode. The corrosion rate is increased by any mechanism that
decreases the diffusion distance or brings fresh solution into contact with the corroding
metal. Hence corrosion is ordinarily faster in flowing water than in still water. Waterline
corrosion of pilings and ship hulls is faster in rough water than in smooth, since waves
constantly wet the surface with fresh solution. The same mechanism tends to make the
corrosion rate in a water spray higher than that when the metal is fully immersed.
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Passivation can be very effective in decreasing the corrosion rate. However, it

may lead to an unexpectedly high rate of corrosion in relatively mild conditions, where
the corrosion potential does not reach the passivation value. It may also lead to an
unexpected and dramatic increase in the corrosion rate when the pH of the solution falls
outside the range of stability of the passive layer. Engineering structures that are
ordinarily safe against corrosion may deteriorate rapidly in an environment in which they
are subjected to an acidic (or also, in the case of aluminum, highly basic) effluent or
when they experience acid rain. Passivation is also ineffective when the corrosion
potential is very high (trans-passive) and may not protect against dissimilar metal
corrosion, particularly when the area ratio is high.
12.6.3 Corrosion protection
Since dissimilar metal contact often cannot be avoided in engineering systems,
and since nominally homogeneous metals contain microstructural couples and are subject
to oxygen potential cells, most engineering systems must be protected against corrosion.
There is an entire industry devoted to this subject. Very many different schemes are
used.
However, almost all effective corrosion protective schemes are based on one of
two basic ideas. First, corrosion cannot occur unless a galvanic cell is established. If the
electrical circuit is broken corrosion stops. The circuit can be broken by insulating the
metal from the ionic solution or by insulating the anode and cathode from one another.
Second, corrosion occurs at the anode in the galvanic cell. One can protect a given metal
part by making it the cathode, either by using an external voltage to reverse the cell, or by
introducing a metal into the circuit that is anodic to the metal of interest and corrodes
preferentially.
Insulation at the metal-solution interface

The common methods that are used to break the corrosion circuit at the metalsolution interface include organic coatings such as paint, inorganic coatings such as
natural oxides or passivation layers, and noble metal coatings such as gold.
The most common protective coating is paint. Insulating organic paints provide
excellent corrosion resistance so long as they are intact. However, they must be wellbonded to the metal surface, and even then may break or spall off the surface because of
mechanical damage. If the paint layer is perforated so that the solution penetrates to the
surface, then metal corrosion may spread under the paint, causing it to bubble and peel
from the surface. Under normal conditions the corrosion under the paint layer is a kind
of crevice corrosion; the solution that penetrates along the paint-metal interface is
depleted in oxygen. For this reason corrosion may spread rapidly after the paint is
penetrated, so it is important to inspect painted structures often and repair any damage.
Some of the best protective paints incorporate chemicals, such as PbCrO4, that act as
corrosion inhibitors. If a PbCrO4 paint is perforated to expose the metal surface,
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Materials Science
Fall, 2008
chromate ions go into solution and react at the interface to produce thin, coherent oxide
coatings that inhibit corrosion. These paints tend to be red-orange to red in color and are
sometimes called "red-lead" paints.
Thicker and more elaborate organic coatings are used to seal microelectronic
devices from moisture. Since these devices contain many dissimilar conductors that are
in intimate contact, they are liable to catastrophic corrosion and must be hermetically
sealed from all moisture. The sealing of electronic devices is made difficult by the fact
that conducting wires or contacts must be provided to supply current to the device. These
must be well bonded to the sealant to prevent the influx of moisture along the wire.
Oxide insulation coatings are of two types: those that are coated on the surface
and those that are formed by natural oxidation processes. A common example of an
applied oxide coating is the porcelain enamel that is often used on carbon steel, for
example, in sinks and bathtubs in the home. Natural oxide protective coatings form
spontaneously on aluminum, chromium and many stainless steels when they are exposed
to air. These metals are naturally passive in mildly corrosive environments, and are
widely used for their corrosion resistance. However, it must be kept in mind that these
metals do not have good inherent corrosion resistance. To the contrary, they are highly
reactive. It is, therefore, important that they not be used in conditions where the
protective oxide may be lost. Aluminum and chromium are liable to corrosion in acidic
media since the protective oxides, Al2O3 and Cr2O3, become unstable al low pH values.
Aluminum is also corroded in highly basic solutions since the nature of the oxide changes
at high pH into a phase that is soluble. Chlorine ions attack both Al2O3 and Cr2O3; the
range of pH over which these oxides are protective decreases in the presence of chlorine.
Materials that passivate at high corrosion potentials can often be protected by
exposing them to a high corrosion potential before service to establish a semi-permanent
passivation layer. This technique is also used with aluminum alloys to thicken and
stabilize the natural oxide coating; aluminum processed in this way is called anodized
aluminum. Other materials passivate, but form a protective layer that is not retained after
the potential has been removed. These materials can be protected in service by
introducing a strongly cathodic material into the circuit, or imposing an external voltage,
so that the anode potential is maintained above the passivation value.
Finally, a structural metal can be protected from corrosion by coating it with a
second metal that seals the surface and does not itself corrode. A common example is
gold coating, which is widely used to protect Ni and Cu contact pads in microelectronic
devices from corroding during the period between their manufacture and their final
assembly. Au is useful because it does not corrode, and can be easily electroplated into a
coherent film on Ni and Cu surfaces. The problem with Au is that it is strongly cathodic
to the metal it is intended to protect. If the Au coating is imperfectly applied, or if it is
perforated for any reason, the result is a strong corrosion couple with a very large area
ratio.
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A second approach that has been developed very recently is to protect the metal
with a thin deposited coating of amorphous metal. The coating can be made in situ by
using ion implantation or laser surface processing to implant a high concentration of a
glass-forming solute (such as P or C in Fe) and rapidly heating, with a laser or electron
beam, to drive the coating into the amorphous structure. Amorphous coatings of Fe
highly doped with P or C have excellent corrosion resistance. They resist corrosion for a
unique reason; since their structures are statistically uniform on the atomic scale, their
surfaces contain virtually no microstructural couples that can form galvanic cells. The
amorphous structure has the additional advantage that it has a relatively high free energy.
If the coating is perforated for any reason, the coating is anodic to the base metal and
corrodes preferentially.
Insulation at the metal-metal interface

It is often desirable to use dissimilar metals in structures that are exposed to the
environment. Examples include bolted or riveted structures, where the bolt or rivet is
made of a different material than the bolted plate, and piping systems, where it is often
desirable to use pipe of one alloy for part of the system and pipe of a second metal or
alloy for another. These systems can be protected from galvanic corrosion by the simple
device of using a sleeve or coupling that is electrically insulating and separates the metals
from one another. Since the metals are not in electrical contact, there is no galvanic
corrosion.
Cathodic protection by a sacrificial anode

The final method of corrosion protection we shall consider is cathodic protection;
the metal of interest is protected by making it the cathode in the galvanic cell. There are
several ways to do this. One of the simplest is to introduce a sacrificial anode into the
system. The sacrificial anode is a metal, usually Zn or Mg, that is anodic to the metal of
interest. If the metal and sacrificial anode are brought into electrical contact in an electrolyte, the sacrificial anode corrodes. The metal of interest is the cathode in the cell, and
does not corrode until the sacrificial anode has disappeared from the circuit. Sacrificial
anodes are attached to many structures, such as ship hulls, buried tanks and others, to
prevent corrosion.
It should be kept in mind that a sacrificial anode is only effective if it is in
metallic contact with the metal it is to protect, and in ionic contact with the electrolyte. A
Mg anode that is attached to the hull of a ship will protect the hull from corrosion by sea
water when it is immersed. However, it will not protect the exposed portions of the hull
from corrosion by salt spray, since a droplet that attaches to the hull does not ordinarily
contact the Mg anode.
A particularly good corrosion protection scheme uses a sacrificial anode as a
coating over the surface of the metal. If the coating completely covers the exposed metal
surface then it corrodes at a very slow rate since it is only subjected to its own
microstructural galvanic couples. Moreover, if the coating is perforated by corrosion or
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Materials Science
Fall, 2008
mechanical attack, then the exposed metal is cathodically protected by the remainder of
the coating and does not corrode.
Two important examples of anodic coatings are "alclad" aluminum and
galvanized steel. "Alclad" aluminum is widely used in aircraft. It consists of a coating of
essentially pure aluminum on a high-strength aluminum alloy. The pure aluminum layer
is anodic to the alloy. So long as the pure aluminum coating is intact, it is highly resistant
to corrosion in its own right, and offers very good long-term corrosion protection.
Galvanized steel is used in many applications for its corrosion resistance, and has
recently become the material of choice for external panels in automobile bodies.
Galvanized steel has a superficial zinc or zinc alloy coating. Zinc is anodic to steel. It
resists corrosion so long as it remains intact on the steel surface, and provides cathodic
protection to the steel if it is perforated.
Cathodic protection by an impressed potential

A second common method of cathodic protection uses an auxiliary electrode of
any type along with a battery or other external voltage source. The imposed voltage
ensures that the auxiliary electrode is the anode, while the metal that is to be protected is
the cathode. This method has the advantage that the anode need not corrode at a
significant rate. The external potential can be chosen so that the anode is passivated, or it
can be made of a relatively noble material so that the anode reaction is an anodic reaction
in the electrolyte (for example, the decomposition of water: H2O O2 + 2H+ + 2e-). A
cathodic protection scheme of this type can function almost indefinitely. The cathodic
protection methods that are used for pipelines and other safety-critical underground
structures are usually variations of this method.
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II Thermochemical

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Materials Science

PART II: THERMOCHEMICAL PROPERTIES

7.3 The Conditions of Equilibrium

7.4 The Thermodynamic Potentials

7.5 The Fundamental Equation

7.6 The Thermodynamics of Surfaces

CHAPTER 8: SIMPLE SOLIDS

8.2 The Perfect Crystal

8.2.8 Thermodynamic properties

8.3 The Random Solid Solution

8.4 Equilibrium Defect Concentrations

CHAPTER 9: PHASES AND PHASE EQUILIBRIUM

9.2 Phase Equilibria in a One-Component System

9.4 Phase Equilibria in Two-Component Systems

Binary Phase Diagrams

9.6 The Solid Solution Diagram

9.7 The Eutectic Phase Diagram

9.8 Common Binary Phase Diagrams

CHAPTER 10: KINETICS

10.2 Local Equilibrium

10.3 The Conduction of Heat

10.4 Mechanisms of Heat Conduction

10.5 Non-equilibrium Thermodynamics

10.7 The Mechanism of Diffusion in the Solid State

10.8 Microstructural Effects in Diffusion

CHAPTER 11: PHASE TRANSFORMATIONS

11.1 Common Types of Phase Transformations

11.2 The Basic Transformation Mechanisms

11.3 Homogeneous Nucleation

11.4 Heterogeneous Transformations

11.5 The Thermodynamics of Nucleation

11.6 Nucleation of Non-Equilibrium States

11.9 Interface-Controlled Growth

11.10 Diffusion-Controlled Growth

11.11 Chemical Segregation During Growth

11.12 Grain Growth and Coarsening

11.14 Martensitic Transformations

11.15 Spinodal Decomposition

11.16 Ordering Reactions

CHAPTER 12: ENVIRONMENTAL INTERACTIONS

12.2 Chemical Changes near the Surface

12.3 Chemical Reactions at the Surface: Oxidation

12.4 Electrochemical Reactions

12.5 The Kinetics of Electrochemical Reactions

12.6 Aqueous Corrosion in Engineering Systems

Part II: Thermochemical Properties

The thermochemical properties of materials govern two kinds of behavior:

where T is the absolute temperature,

where P is the mechanical pressure, and

and hence that

Properties of the statistical entropy

and the statistical entropy is additive.

The statistical entropy of a solid of given energy

Sc = k ln() = k [ln(N!) - ln(NA!) - ln(NB!)]

This expression can be simplified considerably by using Sterling's Approximation,

Sc = k [N ln(N) - NA ln(NA) - NB ln(NB)]

where x is the atom fraction of component A, x = NA/N.

Low-temperature behavior: the Third Law

7.3 THE CONDITIONS OF EQUILIBRIUM

Fig. 7.2: Illustration of four kinds of equilibrium: metastable, unstable

By eq. 7.5 the total entropy change in the process is

Since energy is conserved (dE2 = - dE1) and temperature is constant (thermal

7.3.3 Non-equilibrium states; constrained equilibria

A familiar example of a non-equilibrium material is a semiconductor that has