Phase Diagrams in Materials Science-Massalski-MetTrans

The 1988 Campbell Memorial Lecture
ASM INTERNATIONAL
Phase Diagrams in Materials Science
T.B. MASSALSKI
The Edward DeMille Campbell Memorial Lecture was established

in 1926 as an annual lecture in memory of and in recognition o f the
outstanding scientific contributions to the metallurgical profession by
a distinguished educator who was blind f o r all but two years o f his
professional life. It recognizes demonstrated ability in metallurgical
science and engineering.
T.B. M A S S A L S K I is Professor of Metallurgical Engineering, Materials Science and Physics at Carnegie Mellon University. A native
of Warsaw, Poland, he came to the United States in 1954, after receiving his B.Sc. and Ph.D. degrees from the University of Birmingham
in England. After a postdoctoral appointment at the University of
Chicago and a brief faculty appointment at the University of
Birmingham, he joined the Mellon Institute in Pittsburgh as Senior
Fellow and later Research Director. He has held numerous Visiting
Professorships and appointments including California Institute of
Technology (1961), Stanford (1962), Oxford (1967), Harvard (1969),
Krakow (1969), Buenos Aires (1971), National Bureau of Standards
(1980), and the Navy Postgraduate School (1983). He received a D.Sc.
degree from the University of Birmingham in 1964 and an honorary
doctorate from the University o f Warsaw in 1973. He is also a foreign
member o f the Polish Academy. Dr. Massalski is Fellow o f A S M ,
APS, and the British Institutes of Physics and Metallurgists. He has
given the Krumb lectures of AIME, McDonald lecture (Canada), Cullity
lecture (Notre Dame), and Hume-Rothery lecture (Oxford). In 1982,
he received the Hume-Rothery award of AIME. He is coeditor of
Progress in Materials Science together with Professor J.W. Christian
and Professor P. Haasen; and he has been editor-in-chief (since 1980)
of the Binary Phase Diagram Evaluations Program, sponsored by the
A S M and NBS. In this capacity, he has been involved in numerous
activities relating to research on phase diagrams, phase stability, and
alloy structures. He is coauthor of several books, including a textbook
with C.S. Barrett entitled Structure o f Metals, 3rd edition. He is
editor of the proceedings of several meetings and symposia and author
or coauthor of approximately 180 papers and review articles. His most
recent research is on phase stability, metastable structures, and massive transformations.
METALLURGICAL TRANSACTIONS A
I.
INTRODUCTION
THIS lecture commemorates the name of Edward

DeMille Campbell, a most eminent American metallurgist and a great teacher. Only recently have I learned
that much of Professor Campbell's pioneering research
and teaching was achieved after he had lost his eyesight.
I feel most privileged and honored today to lecture in
memory of a man who showed so much courage and
determination in pursuing his profession.
My first exposure to the field of phase diagrams was
as a student of metallurgy at the University of Birmingham
in England, shortly after World War II. At that time,
almost all of us students and the majority of professors
were ex-servicemen types. Not surprisingly, my imagination was caught when the lecturing professor introduced the concept of phase diagrams as "the graphical
result of a battle for survival between competing phases."
The phase diagram was simply a statement of who won
under different battle conditions. Translated into free
energies, thermodynamics, quenching and heating operations, etc., this vivid concept has never been more
true than today.
In the context of materials, there is probably no other
broad subject that impinges more on the various aspects
of materials science and technology than the description of phase stability in terms of temperature and composition. I am certainly not the first to point out that
phase diagrams are the "road maps" that guide and
direct us to our numerous g o a l s - - i n fabrication, development, heat treatment, properties, alloy design, and basic
VOLUME 20A, AUGUST 1989-- 1295
understanding. This interdependence is not new. In

looking over the material for this lecture, I was fascinated to see again and again how much was already
understood and known at the beginning of this century.
I should like to divide this lecture into four parts dealing with the thermodynamics, phase stability, metastability, and assessment of phase diagrams. Each field has
grown to be very large over the years, with contributions
by hundreds of people. So I hope that I may be forgiven
if I comment only on certain aspects of each field that
touch more closely on some of my own work or that of
my students and associates.
Liquid
~', TIx0~
..............
Tg
--T
at%B
(at
II. P H A S E D I A G R A M S
AND THERMODYNAMICS
A. Basic Parameters
Tradition often has a strong influence on the development of a research field, and this is especially true in
the area of phase diagrams, which has tended to be roughly
divided into two subareas. On the one side are metallurgists, solid-state physicists, and materials scientists who
study phase equilibria through various experimental means
that identify the phases present, their composition and
proportion, and their properties, followed by attempts to
understand the ground state energies of such phases and
their behavior in the microstructures of materials. On the
other side are various disciplines in the wide area of thermochemistry and thermodynamics of phases whose aims
are to measure, understand, and model the thermodynamical properties of phases and the connections between
thermodynamic properties, free energy considerations,
and the laws governing phase equilibria.
In a recent foreword to a symposium on computer
modeling of phase diagrams, Bennett I~ remarked that
while at the end of the 1970's the two areas "unfortunately were still represented by two diverse communities, this is no longer the situation near the end of the
1980's." The studies of connections between phase diagrams and the thermodynamical laws that govern them
now date over several decades. Such connections have
become more striking as computer modeling has been
applied to phase diagrams, predominantly in the form of
computer thermodynamic optimization, as formalized in
the CALPHAD (CALculation of PHAse Diagrams) organization and in the journal of the same name. A clearly
evident need for detailed discussions of phase relationships in terms of competition for phase stability based
on thermodynamic functions is also evident in the numerous phase diagram evaluations now being published
in the Bulletin of Alloy Phase Diagrams, which started
publication at the beginning of this decade.
The important connection between phase diagrams and
thermodynamics can be illustrated by reference to
Figure 1. This shows a typical binary diagram involving
an intermediate phase and some primary solid solubility
with respect to each component. The corresponding
schematic free energy picture at a relatively low temperature below both eutectics is shown in Figure l(a).
The knowledge of free energy considerations even at one
temperature can be very helpful when assessing the possible reactions that can occur in this system under dif1296--VOLUME
20A, AUGUST
1989
G
Liquid ~
at%B
(b)
IX
at%B
(c)
Fig. 1 - - P h a s e diagrams and free energy. (a) A schematic binary phase

diagram involving two eutectics and a congruently melting intermediate phase. (b) and (c) Schematic free energy curves at temperature T.
ferent applications. For example, it can be concluded that

if the formation of the intermediate phase y on cooling
from the liquid can be suppressed by preventing the nucleation and growth of this phase through rapid quenching, the phase diagram will be transformed into a
metastable form (Figure 1(c)) where the liquid phase enters into equilibrium with both primary solid solutions.
If this liquid phase can be prevented (again kinetically)
from crystallizing on cooling, a range of amorphous solid
solutions will be obtained below the glass transition temperature marked as Tg in Figure l(a). The depression of
the free energy curve for the liquid in the middle of the
diagram provides a hint that even without liquid quenching, there is a potential in this system for amorphous
phase formation by other means, such as vapor deposition or via solid-state reactions between the pure components. Also, there is always the possibility that the X
phase could be formed as a metastable structure if the
a-phase solid solution is prevented from crystallizing by
a suitable process. Similarly, as I shall discuss later, the
knowledge of the To, T~,, and Tg curves superimposed on
the phase diagram phase fields offers additional information about the relative stability of the phases present
in this system and about the possibilities for manipulating various metastable situations through appropriate heat
treatments and techniques. Not surprisingly, such additional information about thermodynamic and kinetic connections is much in demand these days when phase
diagram information is being assembled and assessed.
METALLURGICAL
TRANSACTIONS
While it is not appropriate to review here all of the

many interesting connections between phase diagrams
and thermodynamics, a subject excellently treated in numerous texts and reviews, it may be helpful to emphasize briefly the order of magnitude of some of the
thermodynamical quantities involved. In its simplest formulation, the free energy, G, of an alloy phase in a twocomponent A-B system may be expressed as in Table I,
which summarizes the thermodynamic approach associated with a regular solution using the familiar notation,
where GA, GB and XA, XB are the free energies and mole
fractions of the pure components, respectively. The change
in the Gibbs free energy caused by mixing the components (AGmix) is illustrated by the graph in Table I. Its
main component is the enthalpy of mixing (AHma), which
is related to the interaction parameter W. Ignoring volume changes, A H m i x represents the change in energy before and after mixing of the two components and ASmix
is the accompanying change in entropy.
In the most basic thermodynamic approach, the socalled quasi-chemical model, it is assumed that the heat
of mixing arises simply' from the differences in bond
energies eAA, eaa, and eAB between the adjacent atoms,
as illustrated in Figure 2 and summarized in Table I. It
can be easily shown TM that in the above formulation, AHma
has a parabolic form with composition and is a function
of the number of atoms per mole (Na), the coordination
number (z), and the bond energy (e), multiplied by the
product of mole fractions. A schematic influence of the
Table I.
Regular solution:
Thermodynamic Approach
= SAG A
q- SaGa +
AGmix
G = SAGA + XBGB + ~XAXB + RT(XA lnXA + XB InXB)

AGrnix = l'~XAS B +
RT(XA lnXA + XB lnXB)

~r
- TASmix
AHmix
AHmix =
PABe
Fig. 2 - - T h e
d i f f e r e n t t y p e s o f i n t e r a t o m i c b o n d s in a solid solution.
magnitude of the ~ parameter on the form of the resulting phase diagram has been elegantly illustrated in a
review by Pelton and Thompson TM for the simple case
when only the liquid and solid phases based on the pure
components are competing, as shown in Figure 3. We
see that a positive or negative value of either f/s or f~L
amounting to several k J / m o l e can profoundly alter the
nature of the observed phase relationships. Similar changes
of magnitude in the interaction parameters of the various
intermediate phases that may also be present in phase
diagrams, coupled with the frequently observed departures from the regular solution behavior, contribute to
the great variety of phase diagrams observed in practice.
As discussed in numerous articles, interaction parameters can be expressed in various ways, often involving
several coefficients which can themselves be functions
of composition and temperature. These parameters and
their behavior must be determined experimentally, or interpolated from existing phase diagram data, or calculated and estimated from various thermodynamical or
quantum mechanical models. Hence, the very large research activity in this complex field.
e =eAB -- ~ (eAA + eBB)

PAB = NaZXAXB
B. T h e r m o d y n a m i c Control o f P h a s e
Diagram Features
bonds mole -l
A H m ix = ~ X A X B
Interaction parameter:
~ = Naze
b
3a
GA
-RT In a B
-RT In aA
IB
~tA
XB
When the representation of phase equilibria is displayed graphically in the form of phase diagrams, it is
necessary to keep in mind the various rules that assure
that the diagrams are constructed correctly. These rules
derive from Gibbs thermodynamics formulated over 100
years ago. [41 For the various specific rules that govern
the inter-relationship between specific topological features of phase diagrams, reference can be made to several publications over several past decades.t5-9] The most
important rule is the Phase Rule, which expresses the
simple relationship that exists between the number of degrees of freedom, the number of phases present, and the
number of independent components in a system. As is
well known, the general condition for equilibrium in a
system containing several components (A, B, C . . . . ) and
phases (a,/3, y . . . . ) is that the chemical potential of each
component must be the same in every phase, as illustrated in Table II.
VOLUME 20A, A U G U S T 1 9 8 9 - - 1297
.QL (kJ mo1-1)

-I0
- 20
-*10
~'20
14oo
L
0
30
1200
.$
.S
IO00
oOO
600
4OO
f L///"~
,o,
_
,.,
_
,c,
,.,
"'
]1o00
t/
\I
I/ /,11
(k)
1400
('l
t200
IOOO
o
:3
o
e00
6oo
~
E
s
(l)
(m)
(n) O
(o)
Xs
_Y S
5L ~
14o0
1200
0000
coo
600
400
(p)
Fig. 3--Regular
(ql
(r)
s o l u t i o n m o d e l i n g . [ P e l t o n a n d T h o m p s o n t31]
A consequence of this set of relationships is the Gibbs

phase rule. It states that for a system consisting of C
components and P phases in equilibrium, the number of
degrees of freedom, F, i.e., the number of intensive
variables such as temperature, pressure, or composition
that can be varied independently, has a fixed value. For
example, for a system of two components at constant
pressure, F + P = 3.
Discussions of possible violations of the Phase Rule
may be found in numerous texts. 19a~ As an example
of the constraints imposed by the thermodynamics on the
possible configuration of a phase diagram, we can mention here a common error that often occurs in representing binary systems having a congruently melting
1 2 9 8 - - V O L U M E 20A, AUGUST 1989
compound between two eutectics, as in Figure 4. Because of the entropy of mixing considerations, I~2~the liquidus has a nonzero slope at the melting points of the
two pure components in a binary eutectic diagram
(Figure 4(a)). However, as Berndt and Diestler i13J have
shown analytically, the liquidus curve must always have
a horizontal tangent at the melting point of a congruently
melting compound, or phase, and the tangent is also
horizontal for the solidus curve. Thus, a phase diagram
with a congruently melting phase cannot be thought of
as consisting of two juxtaposed simple eutectics as in
Figure 4(b), but must be drawn as in Figure 4(c). This
means that if a congruently melting compound exists in
a system A-B, additions of very small amounts of either
Table II.
The Phase Rule*
Thermodynamical Condition for Equilibrium

~X = ~
= g~ = ...
g7~ = g ~ = g ~ = . . .
g ~ -- ~ g = g ~ = . . .
/z -- chemical potential
Gibbs Phase Rule
@ constant pressure
two components
P + F = C + 2 P = phases
P + F = C + 1 F = degrees of
freedom
P + F = 3
C = components
A
(a)
Gibbs-Konovalov Equation
aT
(X~
-- XA)TGxx
AH~
0X caoexist
02G~,
GL--~X~)~AH~p --= m o l a r enthalpy o f first precipitation o f / 3 from

*Goodman, Cahn, and Bennett r~4j
A or B elements to the compound will neither lower the

melting point nor raise the freezing point.
The solidus trend for highly stable or highly ordered
phases can, however, appear sharp. As a general rule,
the solidus curve will be broad for weakly interacting
systems and narrow for strongly interacting systems. Thus,
even though thermodynamics requires a horizontal slope
at the melting maximum, the solidus can sometimes appear pointed. In the absence of thermodynamic data, one
can estimate that the solidus will appear pointed for phases
of very limited nonstoichiometry. [14] It is unfortunate that
in many published phase diagram evaluations, some of
the most simple rules like the one above are often relaxed, or forgotten, leading to incorrect representations
of important phase diagram features. Similar attention
must be paid to numerous other topological features. Recent papers by Goodman e t a / . I141 and Allen and Cahn I~Sj
discuss several important points derived from thermodynamic principles. Goodman et al. have shown that the
slope of the coexistence curve between the phases a and
/3 in a binary system A-B at constant pressure may be
expressed as shown in Table II, where X~, is the mole
fraction of A in the a phase, A H ~ is the molar enthalpy
of first precipitation of an infinitesimal amount of the/3
phase, and G ~ is the second compositional derivative of
the free energy of the a phase. This Gibbs-Konovalov
equation, as it has been named, not only provides an
identical conclusion regarding the tangents at the congruently melting phases and compounds, but can also be
used to elaborate the rules in connection with phase
boundary inflections, retrograde solubility, the shape of
coexistence curves in solid-liquid equilibrium, and the
details of the well-known Vant Hoff's equation.
C. Computer Representation o f Phase Diagrams
Before the recent explosion in computer assisted graphic
displays, the representation of phase equilibria entirely
B
(b)
(c)
Fig. 4 - - P h a s e diagram errors: (a) simple binary eutectic; (b) incorrect; and (c) correct. [Bemdtt~2q
depended on visual rendering of phase diagrams, usually

communicated as line-drawn pictorial objects, tm,~lj For
the ternary and higher-order diagrams, the visual comprehension of the various features clearly depends on the
skill with which such diagrams can be drawn and presented, either in an "exploded" form, I~~ perspective
form, tH~ or with stereographic aids. [~61In the latter case,
a three-dimensional ternary diagram is represented in the
form of two sets of perspectively drawn diagrams, one
in red and the other in green, to be viewed with red (left
eye) and green (right eye) glasses, thus rendering an excellent three-dimensional simulation. Numerous examples of "exploded" ternary diagrams are found in the books
by Rhines tl~ and Prince. [m They provide a very helpful
aid in the understanding of such systems.
A simple ternary phase diagram, based on a binary
system with a complete solid and liquid miscibility and
two binary simple eutectics, is reproduced from Rhines'
book in Figure 5. (This diagram, incidentally, is the diagram used as a motto for the ASM/NBS Phase Diagram
Program [see Section V], and it has also found its way
onto the ASM phase diagram tie that some of you may
be wearing today.) An example of the "exploded" portions of the ternary diagram into component phase fields
may be seen in Figure 6(b).
It is natural to expect that the growing computer technology, both in terms of programs available for direct
calculations and the various graphics programs, should
lead to an increasing use of computers in phase diagram
display and phase diagram representation.
Early work here, dating back about 20 years, involves
Russian contributions, [17,18,19]stressing the concept of information retrieval systems based on topological and analytical representations of phase diagrams or portions of
phase diagrams. Binary phase diagrams and later ternary
and multicomponent phase diagrams have been generated in terms of graphic displays through various programs at the National Institute of Standards and
Technology, t2~ and elsewhere. [22-251
Such graphic displays and the related computer software are sometimes coupled with thermodynamic models
for calculating phase boundaries, or are merely treated
as mathematical representations of topological features
associated with a given phase diagram system. The objective here is to replace the draftsman, at the same time
guarding against topological errors by worrying about
self-consistency, and also finding out how computers enable us to produce complex sections, tie-lines, enlarged
portions, and other interpolated features. The various

differences among digital, analytical, topological, and
thermodynamic methods have been recently discussed
by Nash. t261Analytical modeling consists of representing
every boundary or topological feature by some polynomial function, from which any point on the boundary
may be calculated. A nice example of analytical representation of boundaries, surfaces, and critical features is
shown by Orser t2~ and reproduced in Figure 6 for the
simple ternary system shown in Figure 5. All of the invariant (point), monovariant (boundary), and bivariant
(surface) elements can now be subjected to mathematical
representation and modeling useful for storing the results
in a computer. Here, the geometry of the phase diagram
can be separated into two types of information: topological and metrical, and all the topological features can be
assigned a metric attribute. Even in this case of a simple
ternary system, the actual decomposition into a hierarchy of volumes, surfaces, edges, and vertices involves
some 70 topological elements, each of which must satisfy self-consistent topological and analytic conditions.
As emphasized by Orser, [21j "the trick is to get such a
decomposition figure into the computer in a simple way."
Of course, such a procedure does not involve phase diagram modeling. The data base will simply store the topological elements of the phase diagram. It will contain
no information on the properties of any of the phases,
unless additional software is programmed for this purpose.
The topological elements in Figure 6(c) are analogous
to the diagrams known to us in the familiar books by
Rhines, II~ Prince, tll] and others, which communicate so
well the "feel" for phase diagrams as pictorial objects.
Two-dimensional sections of ternary diagrams and various other features are now generated routinely by computer in several diagram development progralTIS. [20,25,27,28]
Further details about the use of computer graphics in the
display of phase diagrams may be found in the recent
symposium, edited by Bennett. m
D. Higher-Order Transitions and Critical Points
Li~uidvs Surfaces
\\
\~
~
Solidus
",
\\
Surf
\Y
I
/
/\
. . . . .
\ ~ - ~
I_ \ ~
- / ~ +#/,/J
~_l_--
Solidus
I Surface
/"-t i
~../ .... ~ \ ~
I Solvus
r'~
Ill
C
Fig. 5 - - O c c u r r e n c e of three-phase equilibrium in a simple ternary
system. [RhinesV01]
1300--VOLUME 20A, AUGUST 1989
Certain phase diagram features in the vicinity of critical points have been considered by Allen and Cahn t~51
and are of particular interest in the case of diagrams involving ordering or magnetic transitions. Changes related to first-order thermodynamic phase transitions
involve distinctly different phases, having different order
parameters, compositions, enthalpies, entropies, and/or
densities. Higher-order transitions are less common, but
when they occur, several phases and domains within some
of the phases become identical in every respect as the
critical point is approached. As a result, there are no
discontinuities in composition, entropy, or molar volume
and, therefore, the free energy and its first derivatives
are continuous at the transition. Nevertheless, higher-order
transitions are characterized by singularities in some
thermodynamic functions at critical points on the phase
diagrams or along critical lines or surfaces. A consolute
critical point occurs when a miscibility gap between phases
of identical structure narrows to a point, as in the wellknown Au-Ni system. In the/3 phase of the Cu-Zn system, the long-range order parameter disappears along a
line of higher-order transitions, where the disordered phase
(a)
~L+~a
(b)
(c)
vs
UI
v~
gt
Fig. 6 - - T o p o l o g i c a l decomposition of a simple ternary. Only the a + /3 phase field decomposed. Actual decomposition contains 70 topological
elements. [Orser t2~l]
and two ordered domains become identical. At a bicritical point, three phases meet, separated by two lines of
higher-order transitions and a two-phase field. At a tricritical point, a line of higher-order transitions merges
with a two-phase field of the same two phases. At a tetracritical point, four phases meet, separated by four lines
of higher-order transitions, etc. These special features of
phase diagrams are attracting increasing attention and are
being increasingly incorporated into critical assessments
of many important alloy systems. Schematic illustrations
of the occurrence of typical critical points have been discussed recently by Laughlin and Soffa. ~29j
A miscibility gap in the solid state also involves the
presence of chemical and coherent spinodal lines, as illustrated in Figure 7. It shows that an alloy of composition C 9 is in a single-phase region at high temperature
(such as T), but may be brought into a two-phase region
at TA, for example, by quenching. As is well known,
two distinct decomposition behaviors can be observed in
the Co alloy quenched from the single-phase region. For
quenches to temperatures just below the solvus line, nuclei of the new phase form from relatively large local
fluctuations of composition. This is the decomposition
path known as "classical decomposition and growth."
With large undercoolings below the spinodal line, the
alloy begins to decompose along paths in which the change
(g
C~o
Miscibility
l
l
/Gap
~ / ' , \ / C h e m i c a l
-"
"-~
S p ~ dal
TA'
/ I/ /
~I iI
A C1
S/
Coherent
Spinodal
....
I
I
A2
T3
B2
a
"L~TS
B2"
of ordered phase
', \
~\ \
%+%
Co
Atomic Fraction of B
C2 B
A
Composition (% B)
Fig. 7 - - C h e m i c a l and coherent spinodal lines. [Laughlin and Soffa1291]
(a)
of composition is small at all locations, but the distance
over which it changes is large. Such a process is known
as spinodal decomposition. Thus, the spinodal line in
Figure 7 indicates an instability with respect to the response of the system to compositional fluctuations small
in magnitude and large in extent. If such fluctuations
also involve elastic strain energy changes within the decomposing alloy, the effective "chemical spinodal" curve
is changed, thus defining a "coherent spinodal" that may
depend strongly upon the imposed mechanical loading
conditions.
Figure 8(a) illustrates a phase diagram having a higherorder/disorder transition involving the bcc structure when
the second nearest neighbor interaction energies are taken
into account. At low temperatures, the equilibrium state
consists of two phases, one of which is disordered bcc
(known crystallographically as A2) and the other which
is ordered, as in CsCI (known crystallographically as B2).
The line of higher-order transitions intersects the miscibility gap at a critical end point. Free energy considerations indicate that the ordered phase at a temperature
T3 is stable at all compositions against a possible phase
separation (Figure 8(b)). However, at temperatures slightly
above T2, a hump develops in the free energy curve of
the ordered phase and with it a tendency toward phase
separation. This phase separation is contingent on prior
ordering of the disordered phase. Therefore, it is referred
to as "conditional spinodal. "~lsl
More complex critical points are relevant in systems
involving the ferromagnetic/paramagnetic ordering of the
magnetic spins superimposed on crystallographic ordering. For a system involving the bcc structure, the four
phases to be distinguished are
A2p paramagnetic disordered bcc solid solution;
A2s ferromagnetic, spin-ordered bcc solid solution;
B2p atomically ordered CsCl-type paramagnetic phase;
and
B2I ferromagnetic, atomically ordered solid solution.
A tetracritical point is a special configuration in which
a "doubly ordered" phase (magnetically and crystallo1302--VOLUME 20A, AUGUST 1989
at T 3
Ck
Disordered
Ordered
A
Composition (% B) - -
(b)
Fig. 8 - - ( a ) A schematic phase diagram o f a solution exhibiting a
critical end point. (b) A schematic free energy v s composition diagram. [Laughlin and Soffatzgq
graphically) becomes stable and the four phases become

indistinguishable, having the same free energy. This is
illustrated schematically in Figure 9 for the Fe-Si system. Actually, a tricritical point occurs at about 13 at.
pct Si, and a tetracritical point occurs where the line of
Curie temperatures crosses the line of order/disorder
transitions.t3~
E. Coherent Equilibrium and "Coherent

Phase Diagrams"
A typical phase diagram depicts boundaries between
fields which correspond to single phases or in which there
are different sets of coexisting phases. When the phases
coexisting in equilibrium are incoherent in the microstructure, the boundary curves in the phase diagram (or
boundary surfaces in ternary systems, etc.) are also
the loci of the ends of tie-lines (and tie-figures) which
mark not only the points (i.e., compositions) where
ap
Te ~paocir~/t~..X
/
/"
B2p
Trip(ci~t~ca1
/B2p + DO3p
- B2f + DO3p
B2f + DO3f
DO3f
Composition(% B)
Fig. 9 - - A schematic of the Fe-Si binary diagram, [Laughlin and
Soffa1291]
each new phase first appears, but also the compositions

of the phases coexisting in multiphase equilibrium. It
has become apparent, however, that these features of
equilibria are not always retained in coherent, stressed
systems, and it is worthwhile to recognize this in the
studies and construction of phase diagrams.
Differences between coherent and incoherent equilibria were first recognized by Cahn [32] in his early treatment concerning the influence of misfit strains on phase
equilibrium in systems possessing a consolute critical
point. For the assumed form of the elastic energy, Cahn
showed that the coherency strains stabilized a single phase
with respect to a two-phase system. The qualitative features of the equilibria, such as the coincidence of the tielines and phase boundaries, were retained. Such shifts
in the phase boundaries are easily displayed on a phase
diagram.
Recent theoretical work r3z-35] has shown that for many
stressed coherent systems, the equilibrium phase compositions should depend on the bulk alloy composition
across a two-phase field. This is the result of the thermodynamic state of one phase being coupled with the other
phases through the elastic energy. Hence, the tie-end
points (and tie-figures) depend on the volume fraction of
the phases present and are different from those established for incoherent phase equilibria. Cahn and Larche t361
argue that the observations of what phases coexist in coherent equilibrium can be useful to establish phase fields
whose boundaries can be depicted on phase diagrams,
but it must not be expected that the measured tie-line
points (i.e., compositions, for example, by X-ray diffraction) will be the same for all volume fractions. Cahn
and Larche [36] further suggest that discrepancies between
various solid-state phase diagram determinations in the
literature may be due to s u c h differences between coherent and incoherent equilibria, depending on the techniques that have been used to measure either the phase
field boundaries or the tie-line end points. Johnson t35~ has
shown that when the elastic states of the phases are coupled, the number of degrees of freedom in a system of
coherent phases will be independent of the number of
METALLURGICALTRANSACTIONSA
phases present, F = C + 1 . . . . . which is in direct contrast to the relationships shown in Table II and demonstrates that coherent solids do not obey the Gibbs rule
for fluids or unstressed systems. Johnson points out that
domains of what may be regarded as being the same phase
in the absence of all stress effects may be associated with
different states of deformation due to coherence and,
hence, may possess different equilibrium compositions.
This implies that any number of distinct phases may be
present together in coherent equilibrium.
If the thermodynamic state of a phase at equilibrium
is independent of the presence of the other phases, the
total thermodynamic potential of the system is equal to
the weighted sum of the thermodynamic potentials for
each of the phases (determined independently of the other
phases). It is this condition that allows the tangent construction to the free energy curves to be related to the
chemical potentials of the individual components and,
hence, serves so well as a graphical representation of the
equilibrium phase compositions and volume fractions.
This condition is usually not met in coherent systems and
the tangent construction is no longer valid. Phase equilibrium in a two-phase region involving coherent phases
is much more complex, because it can be demonstrated f371 that a number of equilibrium states (combinations of volume fractions and phase compositions) may
exist that yield energy minima for a given combination
of temperature, pressure, and alloy composition. In fact,
there may be discontinuous jumps in precipitate volume
fraction even when the alloy composition is varied
smoothly across a two-phase field, These coherent elastic effects are often difficult to display on a phase diagram, but the potential shift in the spinodal curve and
the critical point, as well as the dependence of the equilibrium phase compositions on alloy composition, can be
illustrated as in Figure 10, reproduced here from Chiang
and Johnson. r38~
Williams t34t has treated coherent two-phase mixtures
and the possible modification of the equilibrium compositions expected as the result of the influence of both
the interfacial and coherency energies. His calculation
shows that in the case of the Cu-Au system near the
1.8
[~oo]
";
e ~.4-
. r
,,
= .
co =
,"
#,'
t"
/
/
/ -"
./
-\
', % ',I
Critical Point . ~
~'E1.2 /
"'-'~"
."
\
"~\ \\\
i ~
/
, / C o = 0.8
,
0.2
0.4
Co = 0.8 ~
,
0.6
0.8
Alloy Composition, Co
Fig. 10--Elastic effects in coherent equilibrium. [Chiang and
JohnsonL38J]
VOLUME20A, AUGUST 1989--1303
composition Cu3Au, the equilibrium two-phase field estimated to be 10 at. pct wide can in fact be reduced by
half through coherency energy of some 21 J / m o l e and
again by half through the contribution of total interfacial
energy of some 8 J/mole. The schematic influence of
these two parameters is illustrated in Figure 11. Williams
proposes that if the contributions of the interfacial and
coherency energies are sufficiently large, the two-phase
field will disappear completely or partially. Clearly, these
effects are likely to be important during interpretation of
experimental data in terms of equilibrium phase relationships. However, one may argue whether or not
interfacial energy should be included in a description
of phase equilibria.
The occurrence of coherence may be expected in
(a)
multiphase mixtures or during precipitation, particularly

when the phases involved differ from one another merely
by the distribution of different types of atoms on the sites
of essentially the same crystallographic lattice, as, for
example, in the Cu-Au system. In such a case, all phases
formed must represent different ordered forms of the
parent disordered lattice. Quite complex phase diagrams
can then be treated theoretically by means of the cluster
variation method. [38,4~
Thus far, mostly equilibria
between phases based on the fcc parent lattice have been
treated in this way, and the calculated phase diagrams
are referred to as coherent phase diagrams. Since all ordered ground states (superstructures) along with their
energies and configurational entropies can be considered
as perturbations of the common reference state (the fcc
lattice), only pair interactions need be considered. Thus,
only the various ratios of the values of the second-tofirst nearest neighbor interactions are the parameters which
enter the calculation. As pointed out by de Fontaine, [39j
practical benefits are expected from such calculations
because, frequently, the metastable phases into which a
disordered phase first transforms, for example, when
quenched, are those derived from coherent phase relations. Some prototype coherent phase diagrams have been
calculated for several systems by a number of authors. [39'41] Nearest neighbor interaction parameter ratios
can also be used to assess phase stability in various layer
structures (see Section Ill-E).
F. Irradiation Effects
AG
Coherency+~
Interfacial ~ B
~
o A"
h
/
'
"
eA"' r
c B" y B
(b)
30
Cu - Au System
20 - -
600 K
] Cu3Au
~ C
/\
"6
,~
/ _2.5%N~ LID SOLUTION
0 L-
I
30
32
34
36
ATOMIC PERCENT Au
38
(c)
Fig. 11--(a) A model of coherent mixture; (b) the modification of
the equilibrium compositions by the interracial and coherency energies; and (c) the effects of interfacial and coherency energies on the
equilibrium in the Cu-Au system at 600 K. [Williams1341]
While the majority of phase diagrams apply to situations in which it is assumed that phase equilibria determined under conditions approaching true equilibrium are
of interest, phase relationships are also often of interest
under conditions that substantially depart from equilibrium, for example, during irradiation. Irradiation of metals produces large numbers of vacancies, self-interstitials,
dislocations, highly energetic atoms, and various possible atomic displacement cascades. As pointed out in a
recent review article by Russell, t42~these species interact
with the microstructure in various ways and can profoundly alter the stability of actual or potential phases.
For example, irradiation tends to disorder an ordered phase
by mixing the atoms on respective sublattices in the
structure, while at the same time, it assists reordering by
providing an enhanced diffusion coefficient. For example, Liu and Wilkes [431 analyzed these effects in the TiRu system and predicted that disordering should occur
most readily at low temperatures. Hence, the ordered
phase at 50 at. pct Ru is expected to become disordered,
altering the phase relationships, as illustrated in Figure 12.
Phase relationships are also expected to be profoundly
altered when materials are present not in the form of
bulk, but, for example, as very fine particles or as thin
surface deposits. In the latter case, special phase diagrams are sometimes proposed which make allowance
for the strong influence of surface and elastic energies,
as in the case of coherence discussed earlier.
G. Thermodynamic Modeling
Since a phase diagram is a representation of the
thermodynamic relationships between competing phases,
5000
o
LIO.
2000
T,K
+
TiRu
+
TiRu
I000
e +TiRu
0
Ti
02
CRu''-~
1.0
Ru
(a)
3000
b
LIQ.
I
2000
T,K
19 ~
~'
+TiRu
TiRu
I000[I
~
0
0.5
CRu~
Ti
I.O
Ru
(b)
Fig. 1 2 - - ( a ) Ti-Ru phase diagram under thermal conditions. (b) TiRu phase diagram during irradiation. [Liu and Wilkes t43j]
the most fundamental approach to obtaining a phase diagram is considering the behavior of relevant free energy
functions for each phase. Here, the free energy for each
phase is generally represented by
G i =f(T,P,X~,X2
.....
X,,)
[1]
where G i is the free energy of the i t~ phase in an

n-component system. The field of coupling thermodynamics with phase diagrams has grown very rapidly
in the last two decades, and numerous references can be
found in excellent reviews. [44-47]
Numerous problems and questions have been and are

being addressed and treated, and progress continues rapidly in many directions. For example, the problem of
how to treat thermodynamically the stability of phases
and compounds, with increasing degree of order, how
to deal with extrapolations to low temperatures, how to
supplement missing thermodynamic data with empirical
modeling or interpolation, which computer programs to
use, and how to establish data banks of thermodynamic
properties with features of high generality are only some
of the questions that are likely to be addressed for some
years to come. As Hillert [47~ points out in a recent review, "the future extension of the (thermodynamic) data
base to cover most of the substances of practical importance will require an immense amount of work." Here,
I shall mention only a few examples of thermodynamic
modeling with which I have recently come in contact.
In addition to intense activity in this country, Sweden,
Germany, England, or France, I have recently seen in
Japan a most promising demonstration of computer calculation of phase diagrams of semiconductor systems by
Nishizawa and his associates. [48] The complexity of the
program is illustrated schematically in Figure 13 and an
example of an isothermal section calculated for the quaternary system Ga-In-As-Sb is given in Figure 14. Clearly,
a data base of this kind and the associated computer software will be of great importance in future developments
of tailored semiconductor alloys and devices.
An example of a phase diagram assessment for a system such as Au-Nd, for which neither phase diagram nor
thermodynamical data exist, involves the possibility of
utilizing information from "adjoining" systems, for whichsome information is available. This is particularly true
for the case of alloy systems involving the rare earth
elements, where it is known that numerous properties
change across the whole series of elements according to
well-recognized and systematic patterns. Thus, for the
rare earth elements alloyed with gold, it is possible to
interpolate the relevant thermodynamic data for Au-Nd
from the adjoining systems Au-Ce and Au-Dy, as illustrated in Figure 15, for the behavior of the A G XS[491 function. The resulting calculated phase diagram is as in
Figure 16, and it is very likely to represent the actual
diagram that has yet to be determined.
A rather different approach is needed for the case when
the phase diagram is well established experimentally as
in Cu-Ga, but where the thermodynamic data are scarce.
Here, we have recently attempted to develop such data
through suitable modeling, [5~ in order to assess the magnitude of the driving force involved during the occurrence of the well-known massive transformation in this
system from the high-temperature bcc phase to the lowtemperature hcp phase, p~] The agreement obtained between the calculated and experimentally determined phase
diagrams in the Cu-rich portion is as shown in Figure 17.
Following from it, it is possible to compare the actual
free energies of the competing phases at a temperature
where the massive phase transformation takes place and
derive the driving free energy for this compositioninvariant change. This is illustrated in Figure 18. It can
be seen that this energy difference is surprisingly small,
of the order of 50 to 100 J/mole. This emphasizes the
fact that the energy differences between the phases that
DBSEMI
(Thermodynamic
database)
PEDIT
I I
SEMLCALCI
(Construction of
phase iagram)
I LP-CALC [
I BAND_CALCI
(Calculation of
lattice parameter)
(Calculation of
band gap)
Alloy system
Alloy composition
Input
- Input
9
Temperature
(editor for
DBSEMI)
Tsothermal section-Vertical section

Liquid composition
equilibrated with
compound phase
Lattice parameter
Band gap
Solid composition
equilibrated with
liquid phase
[
=
Graphic representation
Hard copy
Fig. 1 3 - - C o m p u t e r
calculation for semiconductors. [Tokunaga, Ohtani, Ishida, and Nishizawa148q
compete in phase diagrams are often very small indeed,

and that extraordinary precision will be needed in assessment of such energies if phase stability relationships
are to be predicted from first principles calculations. It
also illustrates the fact that phase stability considerations
are of prime importance in the understanding and prediction of phase diagrams.
lnAs
III.
PHASE STABILITY C O N S I D E R A T I O N S
A. Introduction
Along with the progress achieved in the measurements

leading to the details of phase diagrams and associated
progress, it is natural that the observed phase stabilities
should be tested against basic theory. Among the many
needs here, two aspects stand out sharply:
(1) The need to calculate phase stability from "first principles" in order to understand the basic parameters that
control the energy of a phase.
(2) The need to utilize the successful theories of phase
stability for predicting phase diagrams in Systems where
k J/tool
zxGxs ~
-t0 -
Gd T b D y H o Er Tm
Lu
I nSb
L
Fig. 14--1sothermal section diagram for the Ga-ln-As-Sb quaternary
system at 873 K. [ T o k u n a g a e t a / . 1481]
!,
.2
.~
.,
.~
.~
!7
.8
~9
XA~
Fig. 15 -
Phase diagrams via interpolation. [Okamoto and MassalskP 491]

Percent
Weight
5oo]
Gold
1600
~-
'~
021~
1000.
;',.,
(pNd)
II
1 'PID~
hd
.,~c 2;-g:.,____..-~...
~J
fl::
(.9
Z
emo~;
.-'~7.3
",/'/
17.11
~oo] I
zoo]
I00 o
'~ a 9 2 / "
400 T
1450~
r-..
, .."~176
1400
~51"r
otO0'
-200 -
tm
-300 "
(Au)~
(.Na)
-400
18
IBI*C
-~b
2'o
Nd
Fig. 1 6 - - C a l c u l a t e d
M a s s a l s k i 1491]
4'o
5o
6'o
;o
Atomic Percent Cold
"
9'o
"%o
Au
"1-
TO
i
EXPERIMENTAL
** CALCULATED
I000
900
800
71:10
- 600
~-
/I
500
4oo
Cu
2'2
~'4
Z6
~'8
Fig. 18--The driving free energy for the massive transformations in

Cu-Ga alloys. [Subramanian et al. tS~
phase diagram Au-Nd. [Okamoto and
CALCULATED C u - G a P H A S E D I A G R A M S H O W I N G
TREND F O R 13- - > r ~ T R A N S F O R M A T I O N
i
ATOMIC PERCENT Go
measurements have not yet been done or are particularly

difficult. Here, progress will ultimately permit technologically relevant complex or multicomponent phase diagrams to be predicted.
It was Hume-Rothery and his associates who more than
a half century ago laid the foundations for a systematic
study of phase diagrams and their interpretation. A suitable testing ground at that time was the stability of alloy
phases based on the so-called noble metals Cu, Ag, and
Au. 152,53] From this work has emerged the emphasis on
three general metallurgical parameters. Stated very
broadly, they are
(1) the difference in atomic sizes of the components;
(2) the "electron concentration" change on alloying; and
(3) the
electrochemical
differences
among
the
components.
Below, I shall comment on the current understanding and
use of these parameters.
Regarding the basic theory, the understanding and
I100
20
ATOM
PERCENT
Go
Fig. 1 7 - - C o m p a r i s o n o f c a l c u l a t e d and e x p e r i m e n t a l p h a s e boundaries in the C u - G a system. [Subramanian, Laughlin, and M a s s a l s k i tS~

prediction of phase stability of alloys and compounds in

terms of the electronic structure calculations is a subject
of paramount importance in materials science. There has
been much progress in the "first principles" (or the socalled ab initio) approach to the band theory of both ordered compounds and, more recently, also of random
metallic alloys. [54] At the same time, because of the
pressing need of technology, many semiempirical or partially qualitative schemes of phase stability have been
pursued, often very successfully. 155-6~ The results of such
attempts are usually the estimated heats of formation
(AHM).
Basic theoretical guidelines are needed to classify phase
diagrams in order to be able to extrapolate from known
binaries to higher-order systems. A theoretical derivation
of energies of specific structures and phase equilibria between them eventually will yield reasonably accurate free
energy and entropy changes and a description of states
of partial order, relative stability of metastable phases,
etc. Clearly, the first step toward true theoretical determination of phase diagrams is to calculate the energies
of phases involved in simple binaries and compare them
with experimentally determined values, where possible.
As pointed out recently by de Fontaine, [39]
"Briefly put, the problem is this: given only the atomic
numbers ZA and ZB, calculate the A-B phase diagram.
Thus posed in all generality, the problem cannot be solved
today. Perhaps, it never will be: although cohesive energies for many pure A and pure B can now be calculated
with great accuracy from first principles, the precision
in energy is only just marginally sufficient to select the
correct crystal structure among the simple bcc, fcc, and
hcp structures."
Not many other structures have yet been treated
successfully.
It would be inappropriate as well as impossible to attempt here any detailed description of the now very numerous theoretical models which have been developed
for the purpose of assessing the stability of different alloy
phases and competition between them as expressed in
phase diagrams. A number of theoreticians in excellent
reviews {6',6z,63l have outlined the different operations that
must be performed to calculate a composition-temperature
VOLUME 20A, AUGUST 1 9 8 9 - - 1307
phase diagram of a binary alloy starting first with the

stability of individual phases. Essentially, these steps are
as those enumerated in Table III.
From the point of view of phase stability, the result
of such a detailed calculation would be a sufficiently precise set of values of the enthalpies of the various competing alloy phases and their variations with composition.
The calculation of the phase diagrams, including temperature and entropy, would be the next step. Clearly,
from the point of view of phase stability, even these initial calculations represent a monumental task. Yet, a
glance at Table IV quickly shows that theoretical assessments are our only reasonable hope of dealing with
higher-order systems in the near future. In Table V, a
brief summary is given of some of the more recent theoretical calculations that have been developed. This
summary is not intended to be comprehensive or complete.
As emphasized by many authors, [53,63,64] the majority
of existing models, from the semiempirical to those providing detailed density maps and electronic parameters
of alloys, have the same major drawback as far as phase
diagrams are concerned: it is difficult to treat theoretically the temperature dependence of the energy. For example, the calculations that predict enthalpies at 0 K (for
Table III.
Phase Stability Calculations*
(First Principles)
General Procedure
(1)
(2)
(3)
(4)
(5)
Calculate self-consistent atomic potentials of components.

Fix alloy composition.
Assume a possible crystal structure.
Choose lattice parameters.
Introduce the atomic potentials on the lattice, calculate selfconsistent band structure and ground state energy, and add
interionic energy.
Result: total energy

(6) Repeat (4) and (5) for different values of lattice constants.
(7) Repeat (3) through (6) for other possible crystal structures.
(8) Repeat (2) through (7) for other compositions.
Result: enthalpy of the possible alloy phases as a function of
composition.
*Lomer,t6q Faulkner,t621and Hafner~63~
Table IV.
Possible Number of Systems
n = number of elements (say 90)

m = number of elements in a system
n!
m!(n - m)!
binary
ternary
quaternary
90~
2!88!
90!
3!87!
90!
4!86!
1308--VOLUME20A, AUGUST1989
= 4,005
- 117,480
= 2,555,190
Table V. Recent Theoretical Calculations

of Phase Stability or Phase Diagrams
Type of
Calculation
Quantities
Calculated
Typical
References
Semiempirical
(charge density,
size, and
electronegativity
effects)
enthalpy of
mixing, AHI
Miedema et al. [561

Miedema and
Niessen [791
Pair potentials
alloy stabilities,
mntransf (at 0 K)
Machlin IH91
Mainly d-band
effects
maps of related
structures and
their stability,
AHf
Pettifor t59,8~
Watson and
Bennett 155,~2~
Yukawa et al. ~sS1
Mainly valence
band effects
relative alloy
stabilities,
density of
states
Mott and Jones t681

Brewer tl21~
Mizutani and
Massalski t531
Cluster variation
models
ordering energies,
order-disorder
AH~ (at 0 K) of
simple systems
de Fontaine 139~
Kikuchi I4~
Antransf(at 0 K)
Yin and
Cohent1221
Freeman et al.I781
Pei et al. [77]
Stocks and
Winter t541
Hafner t63~
Terakura
First principles
calculation
using various
atomic
potentials:
DFT, LSDA,
KKR-CPA,
LMTO
lattice dynamics,
ordered
compound
stabilities
simple phase
diagrams
Williams et al. tS~l
et a l . I75'761
first principle calculations) or at some undefined temperature (for the semiempirical models) rarely provide
sufficient information about the thermal behavior of such
enthalpies or the thermal entropy contributions. Yet, for
the purpose of phase diagrams, the Gibbs free energies
must be calculated by adding to each enthalpy derived
from the static models the vibrational energy and the
thermal entropy contributions. The latter, in rum, consist
of vibrational and configurational parts. It is clear that
the prediction of entropies, particularly for possible
metastable phases in phase diagrams, will become the
necessary step before the full potential of the theoretically calculated stabilities can be utilized. Only a few
interesting examples of phase stability, compound stability, and phase diagram calculations are reviewed below
and only as they pertain to the specific future potential
for prediction of phase diagrams.
B. Hume-Rothery "Electron Phases" and Systems
Based on the Noble Metals
The stability ranges and various properties of the phases

encountered in the systems based on the noble metals
are of special interest with respect to the electron concentration parameter ( e / a ) , (here e is the number of conduction electrons [if the d electrons are ignored] and a is
the number of atoms). We may divide the phases (a, /3,
Y, if, and e) into two groups: the primary solid solutions
(a phases), having the fcc structure found in the noble

metals themselves, and the intermediate phases (the/3
phases having the bcc structure, the y phases with the
complex cubic structure, and the numerous hcp ff and e
phases). This is illustrated in Figure 19 for a general phase
diagram based on the noble metals alloyed with the polyvalent/3 subgroup elements of the periodic table. It appears that while the e/a parameter is indeed important
in the a phases, as was thought by Hume-Rothery, [651
their stability ranges are also very strongly influenced by
additional factors. For example, each particular range
strongly depends on the type of crystal structure that follows a given a phase in a given phase diagram as would
be expected from phase competition, t521 In addition, it
has also been shown by Ahlers [661 that the configurational cohesion energy part in the a phases, related
to the third nearest neighbor interactions, constitutes a
large additional part of their total energy. Configurational energy is the difference between the ground state
energy (at 0 K) and the heat of formation. While this
complicates the simple original picture of a-phase stability in terms of e/a (and the related notions connected
with the density of states [N(E) and Fermi surfaces)], [53]
there is outstanding agreement between the experimentally determined behavior of the electronic specific heats
(from which the density of states at the Fermi level can
be derived) and the predicted density of states obtained
from a parameter-free calculation based on the KKR-CPA
approximation. I671 This means that the electronic structure of the a phases is now well understood and the path
is set for a detailed stability calculation of these phases
in the near future.
In the case of the intermediate phases, the situation is
more similar to that originally conceived by HumeRothery (651and Mott and Jones. c6s] Here, the typical electron phases are/3,/z, if, y, and e. A study of these phases
has been a research field in which I have done a great
deal of work myself. In the first place, the simple electron concentration rules conceming the ranges of observed stability are obeyed very well in all of these
intermediate phases, as if a "rigid band" behavior related

to a simple e/a parameter was indeed valid. Secondly,
the details of the Fermi surfaces and the density of states
trends that have been worked out from changes in the
physical properties that are less directly related to the
band structure, such as the axial ratios [52] or magnetic
properties, [69J have now been confirmed by much more
direct and powerful techniques, such as electronic specific heat measurements [53] and positron annihilation experiments. [7~ These experiments confirm that the
assumption of a reasonably sharp Fermi surface in disordered alloy phases is a realistic one. An example of a
striking agreement between a very simple band structure
calculation of the density of states trend for a typical
y-brass structure and the corresponding experimental
measurements related to the density of states t7~] is shown
in the Cu-Zn system as reproduced in Figure 20. Here,
the N(E) curve has been derived from a "multicone"
model. [53] The agreement leaves little doubt that the band
structure picture must be correct. A similarly striking
agreement between a band structure calculation and experimental data has been obtained for another group of
Hume-Rothery electron phases, the /x phases with the
fl-Mn structure. Such studies confirm not only that the
Fermi surfaces associated with Hume-Rothery phases must
be nearly spherical (i.e., nearly free electron), but also
that the coincidence of the stability ranges of these structures with a proposed Fermi surface-Brillouin zone (FsBz)
interaction is not accidental, but holds a vital clue indicating that the variation in the Fermi energy in this
case is the main parameter responsible for stability.
In the case of the hcp "electron phases," the Japanese
w o r k e r s [72,73] confirmed with positron annihilation techniques the major features of a complex Fermi surface
designed by Massalski and Mizutani to explain the e/adependence of the lattice parameters and specific heats.
This follows directly from the early work of Jones I741involving a model of interaction between a nearly spherical (i.e., nearly "free electron") Fermi surface and
specific Brillouin-zone boundaries of the hcp structure
0.9
/
0.~
0.7
c~
tcc
O~
o
O'C"
E
O.Z,
hcp
0.3
2
Cu
Ag
Au
0.2
0.1
electron concentration
Fig. 1 9 - - T y p i c a l alloy phase diagram characteristic of the noble metals.

[Massalski and Mizutani Is3j]
O.S
1.0
electron
15
2.0
concentration
Fig. 2 0 - - D e n s i t y of states values calculated for 3' brass and experimental values due to Veal and Rayne. [Massalski and Mizutani 153] ]
to explain the stability of these phases. The most likely

shape of the Fermi surface is like that shown in
Figure 21(a) corresponding to a Ag-A1 alloy having a
nominal e/a of 1.57. In Figure 21(b) are shown the crosssectional contours of the Fermi surface determined for
the same alloy by Koike et a1.[731The agreement is again
quite remarkable. It is from correlations of this kind that
one is encouraged to speculate about the phase stability
of Hume-Rothery "electron phases" in terms of the differences in the Fermi energy of the conduction electrons.
Utilizing the density of state trend for 3' brass, similar
to that in Figure 20, and another density of states trend
corresponding to the Fermi surface contours of the hcp
~" phases as shown in Figure 22(a), Massalski and

Mizutani [53[ attempted to evaluate the possible phase
competition between the 3' and ~ Hume-Rothery phases
based only on the respective N(E) curves. The result is
shown in Figure 22(b). Here, as indicated in Figure 22,
the difference in the respective energies of these two
phases is expressed in terms of the Fermi energies alone.
Although each term amounts to some 105 c a l / m o l e for
the case of the noble metal alloys, the difference
Atr~-'r
~,e~ is generally reduced to the order of 102 c a l / m o l e ,
which is merely 0.1 pct of the total electronic band structure energy. There are, however, other factors which must
clearly affect the N(E) curve as the crystal structure
changes. This includes, for instance, the presence of the
d band in the middle of the conduction band, as well as
the magnitude of the atomic volume, which affects the
shape of the parabolic part of the N(E) curve near the
bottom of the band. A change in the d-band configuration accompanying a structure change will most certainly
change the value of Uet. A very small difference in the
atomic volumes between the competing phases easily
creates an appreciable contribution to AU~j. Therefore,
only if all other factors cause no appreciable net effect
as a whole on Uet can one consider the changes in the
N(E) curves associated with the FsBz interactions as
N;(E)dE - k E~ Nv(E)dE = 2oo cal/mole
= ;o
i.e. 0.1% of total electronic

band structure energy
(a)
6r
0.3
4
.0.2
(a)
0.1
2
~0
0.S
~300
1.0
1.S
200
7,oo r
-100
(b)
Fig. 21 --Fermi surface topography in a hcp Hume-Rothery electron
phase alloy: (a) predicted [Massalski and MizutanP3q and (b) measured by positron annihilation. [Koike, Hirabayashi, Suzuki, and
HasegawaEv3J]
1310-- VOLUME 20A, AUGUST 1989
(b)
.2ooi_
~,d.
-300 L
05
eleclron
A
1.0
concentration
1.5
Fig. 2 2 - - ( a ) and (b) P h a s e c o m p e t i t i o n b e t w e e n the 3' and ~" H u m e Rothery phases based on the N(E) curves. [Massalski and M i z u t a n P 3]]
holding the key role in determining the relative stability

between the competing phases. Nevertheless, the plot for
A Uet in Figure 22 shows that the steep declining slope
of N(E) in the 7 phase is undoubtedly responsible for
the observed minimum in the energy difference. This
figure also illustrates how a gain or loss in the density
of states affects the values of the relative stability. Despite the fact that no first principles calculations currently exist for these phases, I am convinced that the
Fermi surfaces and the density of states pictures, as
developed on the basis of various experimental observations, are essentially correct. At least in the case of
Hume-Rothery electron phases, the stability ranges and
other features so strongly depend on e/a that I am led
to conclude that all other factors as a whole exert little
net effect on the relative competition for stability.
priate solutions of the Schr6dinger equation. For pure

metals and certain ordered alloys, the advances of recent
years have been quite rapid, as various computational
methods in terms of quite complex software programs
have been developed.
Significant progress has also been reported recently in
the ab initio (i.e., from first principles) assessment of
phase stability in the case of the inter-noble alloy systems Cu-Au, Ag-Cu, and Ag-Au, where the nominal
electron concentration does not change.
Terakura et al. [75'76] in Japan have demonstrated that
the first principles band calculations account very well
for the completely different forms of the three phase diagrams observed in these alloy systems. They also emphasize that in this particular case, the d band is essentially
filled, so that tight-binding schemes for coherence energy calculations, useful for the treatment of the transition elements, are not really convenient; yet, the effects
of s-d hybridization are important and, apparently, so are
the details of the density of states at the Fermi level. In
the Ag-Cu system, the size difference between the A g
and Cu atoms is, of course, important.
The phase diagrams for the inter-noble metal systems
are shown in the upper portion of Figure 23, while the
calculated heats of formation for both ordered and disordered situations are shown in the lower portion of this
figure. These results are in very good agreement with
the observed phase diagrams. In Cu-Au alloys, ordered
C. First Principles Calculations

The objective of the most basic approach to alloy phase
stability is to understand the energies and the physical
properties of materials in terms of the elementary building blocks of matter, nuclei, and electrons. Thus, we are
interested in theories which involve calculations that are
"first principles," that is, without recourse to adjustable
parameters. Ideally, as mentioned above, the only input
parameters should be the atomic numbers of the constituent atoms. From there, we should proceed to appro-
(c)
(b)
1000-
zo
1400
100(3
4~
I--
-.-.
500
II
9
500
I"
'
'
'
Ag 0.2 0.4 ~6 o . 8 c u
Cu 0.2 0.4 0.6 0.8 Au
I AI~'~'O.. I
004
d"
<i
"-"
w
0'
0 0 2 " (c)
0.02
--. 0 0 1
"I.O
~
XAu
XCu
0,02 "(a)
Ag 0.z 0.4 0.6 0-8Au
.-. (3.01
d"
,,a _ Q02
-0.01
9
-OO2
I
0.(
0.5
XAu
Fig. 2 3 - - I n t e r - n o b l e
-Q02
-tX~
I
1.0
0.0
(3.5
1.0
0.0
XCu
*
I
(15
XAu
tO
m e t a l s C u , A g , A u . F i r s t p r i n c i p l e s c a l c u l a t i o n . [ T e r a k u r a , O g u c h i , M o h r i , a n d Watanabet75q
VOLUME 20A, AUGUST 1 9 8 9 - - 1311
phases are favored as observed, and the miscibility gap

is clearly indicated in Ag-Cu by the positive values of
AE (i.e., AH at 0 K) at all compositions. In the Ag-Au
system, AE is mildly negative, indicating a preference
for complete solid solubility, again as observed. A detailed comparison with the experimentally measured enthalpies in these systems is given in Reference 76. As
far as I am aware, the only actual phase diagram calculation from first principles is that due to Hafner, ]631
shown in Figure 24. As can be seen, the essential features have been reproduced but not the invariant
temperatures.
The increasing availability of "supercomputers" has
opened up new possibilities for first principles calculations which require a very large amount of computing.
During the past year, we have attempted a comparison
of energies of two crystal structure modifications (L12
and D022) in which the compounds C03Ti and Ni3V are
likely to occur, using the so-called LMTO (Linearized
Muffin Tin Orbitals) approach.j771 The result is shown in
Figure 25. In each case, the correct structure is shown
to have the lower energy at 0 K. Again, the energy difference is but a small fraction of the total energy. More
of such detailed calculations are likely to be reported in
the near future, t78]
D. Semiempirical Schemes
Miedema and coworkers [56'79] have developed a very
useful semiempirical scheme for calculating heats of formation (AHM) of binary alloys. Their scheme supplements earlier attempts by Pauling to relate such quantities
THEORY
800
600
O
2oo0
EXPERIMENT
600
Ca
Mg
Fig. 2 4 - - " F i r s t principles" phase diagram calculation. [Hafner t63J]
to the square of the electronegativity differences.

Miedema's scheme supplements the negative electronegativity term by a positive repulsive contribution
proportional to the square of the mismatch of the cube
root of the charge density at the Wigner-Seitz sphere
boundary. Subsequently, elastic effects have also been
added.t791
The microscopic origin of the attractive and repulsive
contributions to the heat of formation has been explained
for transition-metal alloys by Pettifor's tight-binding
scheme, tS~ which treats the kinetic, exchange, and correlation contributions. Pettifor's theory has been substantially supported by Williams e t a / . t81] with more
elaborate first principles calculations. However, Hafner t631
is concerned that the simple AH calculation schemes neglect the structure-dependent potential contributions.
Miedema's and Pettifor's systematic treatments of a
very large number of systems, phases, and compounds
have found a wide response in the metallurgical and materials science communities. They introduce rational order
where semichaos existed before. They have found numerous immediate applications in predicting unknown
phase diagrams, locating new structures, assessing metastable situations, etc. Most important of all, they point
out the direction in which the basic theoretical calculations should go.
An example of the usefulness of Pettifor's approach
is illustrated in Figure 26. Here, a phenomenological
chemical scale in terms of X is allocated to all elements
in the periodic table in such a way as to achieve a
"structural separation" of all compounds of a given stoichiometry into recognizable groups, as shown schematically in Figure 26(b). To achieve this, elements must
follow a sequence in the periodic table, as indicated in
Figure 26(a). Hence, they may be imagined to follow
along a string ("Pettifor's string"). Excellent separation
of similar structures has been achieved in this way for
numerous phases with a given stoichiometry within single two-dimensional structure maps (XA,EB)"
Prediction of relative solubility and the occurrence of
phases and compounds, mainly related to the various applications of the Hume-Rothery rules, has been also pioneered by many others ]82-86] including work in the Soviet
Union, mainly by Savitskii and his associates, t871The latter
have adopted computer methods to produce "prediction
tables" on the occurrence of three forms of stoichiometric compounds, AB, A2B, and A3B, as well as seven
types of crystal structures common in metallic systems:
Laves phases, CusCa, A15, o'-phase, CsCI, NiAs, and
y brass. In their book published in 1977, Savitskii and
Gribulya claim that "as of January 1976, about 15,000
binary compounds had been predicted, about 2000 had
been substantiated by experimental data and approximately 150 compounds had still not been confirmed."
As an example, in Figure 27, a histogram of predicted
frequency of formation (n) of binary cr phases is shown
in terms of the atomic numbers of the components.
E. Stability of Layer Structures

Ordered close-packed structures are often encountered
in intermetallic compounds of various stoichiome-
Co3Ti
Ni3V
t'r
t/"
O'x
tr~
t"q
-t-
,+
/
DO22
%
"~J
."
tr)
tr~
t'-q
v,,-4
o
4...a
dr"
/
s
9
DO22
t"-vtD
O',
, -3
,+/
lllillliillllillllillllilllll
-2
-1
llli
-3
-2
InilillilliailSililliin
-1
% deviation from experimental lattice spacing 9

AEtota 1 -- 17 - 27 mRy - 0.01% of Etota 1
Fig. 2 5 - - C a l c u l a t i o n
of compound
s t a b i l i t y f r o m first p r i n c i p l e s u s i n g L M T O .
tries, tsS~ An example may be provided by the A3B-type

compounds formed in transition-metal alloys. The IVAVA elements usually substitute for the B-component in
such alloys and the VIIIA elements for the A-component.
The close-packed layers involved in stacking can be either
the triangularly-ordered type (T-type, e.g., like the {111}
plane of Cu3Au ) or the rectangularly-ordered type
(R-type, e.g., like the (112} plane of Ni3V). These layers
are illustrated in Figure 28. Other intermediate ordered
types, such as Tr, Tr2, and Tr4, are also possible. Even
with a fixed-layer type, further structural modifications
can still be made by changing the stacking characteristics
of the close-packed layers. In addition to the simplest
[ P e i , S t o c k s , a n d M a s s a l s k i t77j]
stacking arrangements, 10 (fcc-type) and 11 (hcp-type),

many other arrangements, such as 33, 22, 31, 21, are
also encountered in alloys. Here, we often use the
Zhdanov symbol to denote a stacking sequence. A " + "
is assigned if the order between a layer currently being
stacked and its previous partner follows the relationship to be expected between any two contacting layers
as in the fcc-type sequence, i.e., A --+ B, B --+ C, or
C--+ A. Otherwise, a " - " is assigned. For example,
the sequence " + + + - - ," or 33 for short, is equivalent to ABCACB. Some of the possible layer structures
are listed in Table VI. The stability of these sequences
appears to depend strongly on composition. Usually,
V O L U M E 20A, A U G U S T 1 9 8 9 - - 1313
Co3Ti
Ni3V
r
t"q
,,+
+"',,, _
~d tt~
DO22 ,,"
,,..+
;i"
tr~
\
c5
(
Illl
"7, -3
I I:tllllilllltllllllllll
|
-2
-1
.!
-3
"
/I
""..._+.."
DO22
IlllllllllilllllllllJlllllll
-2
-1
% deviation from experimental lattice spacing.

AEtota 1 =
17 - 27 mRy --- 0.01% of Etota 1
Fig. 25--Calculation of compound stability from first principles using LMTO. [Pei, Stocks, and Massalski [77]]
tries. [88j An example may be provided by the A3B-type

compounds formed in transition-metal alloys. The IVAVA elements usually substitute for the B-component in
such alloys and the VIIIA elements for the A-component.
The close-packed layers involved in stacking can be either
the triangularly-ordered type (T-type, e.g., like the {111}
plane of Cu3Au ) or the rectangularly-ordered type
(R-type, e.g., like the {112} plane of Ni3V ). These layers
are illustrated in Figure 28. Other intermediate ordered
types, such as Tr, Tr2, and Tr4, are also possible. Even
with a fixed-layer type, further structural modifications
can still be made by changing the stacking characteristics
of the close-packed layers. In addition to the simplest
stacking arrangements, 1_0 (fcc-type) and 11 (hcp-type),

many other arrangements, such as 33, 22, 3_1, 21, are
also encountered in alloys. Here, we often use the
Zhdanov symbol to denote a stacking sequence. A " + "
is assigned if the order between a layer currently being
stacked and its previous partner follows the relationship to be expected between any two contacting layers
as in the fcc-type sequence, i.e., A --> B, B ---> C, or
C----> A. Otherwise, a " - " is assigned. For example,
the sequence " + + + - - ," or 33 for short, is equivalent to ABCACB. Some of the possible layer structures
are listed in Table VI. The stability of these sequences
appears to depend strongly on composition. Usually,
1A
lib
cl
llln IVll Vll

t-%
,'i
VIB
VIIB
~5 ,oo ,0, ,o__

IIA Ilia
3
I
lr
II
10
I
l
IVA
16
I
19
I
51
I
Ca
Sc
li
t
I
15
I
Kr
lib
St
II
49
YI
5O
~' ~ 'r "i' 715 ~
LJ o, ~ d
.,
tl
n..
\1
i,-L;t
ix,
A<,
ob
.g
li
~,
vb
r.o
dd
At
33
32
31
3o
29
28
l~
26
La - C e - - P r ~ Nd - I~n ~
S m J ' ~ ' ~ "~- (;,d - - l b - -
48
43
47
46
45
44
--TII - - P,i~i- - tl - - I ~ ' l - - P i l l - -
42
41
40
illllll ~ C l t l - - n k ~
24
23
22
- I)y ~ 1 1 o ~ [ r
39
38
~r~[s-
37
II
~'o k
~ lm/~-~-36
35
Lu T
34
rm - - H ( J - N o ~ L I -
(a)
ZA
//"
El
CsC1
Phase separation o f
A B types.
//
ZB
/
/
mine
Io
,/J
89
[ P
Na
Fe
Ca
04
099
,,6
Ag Au
1.18 1.20
B
2.0
H
5
(b)
Fig. 26--Pettifor's phase separation. [Pettifor1591]
several intermediate sequences can occur before any layertype change takes place. As an example, in the alloy
systems "Fe3V'-CoV-Ni3V and CoaTi-Ni3Ti"Cu3Ti, " a
series of structures based on T-type layers is observed:
10 ---> 33 --~ 22 (or 31) ---> 2_1 ---> 11. This is depicted
1314--VOLUME20A, AUGUST1989
schematically in Figure 29. It is possible to correlate empirically the general trend of such stacking changes with
the "average group number" or the size difference between the A- and B-atoms. t88,89"9~ Yet another approach
is to consider the observed stacking changes in terms of
,ol
20
Nb
Tc
V Mn
Re
Fi
Os
1
,._D_
Tc
ZA
It
Ra
10
70
50
30
90
Zs
Fig. 2 7 - - H i s t o g r a m of frequency of formation (n) of a binary o" phase

by elements. ZA and ZB are atomic numbers corresponding to components A and B. (Open bars, as predicted; solid bars, as observed.)
[Savitskii t871]
interactions between a few adjacent layers as if they were

near-neighbors in an Ising-type modelJ 9~] In this treatment, the interaction between any two layers is solely
determined by their relative positions. In terms of the
conventional ABC notation, we may define a few
parameters.
perimentally observed sequences can be related to a given

path on the stability map and interpreted in terms of the
magnitude of the interlayer interactions. As shown in
Figure 30, the vanadium-based series is reproduced by
the R path on the stability map and the titanium-based
series by the S path. This type of approach clearly shows
that a sophisticated consideration of nearest neighbor
forces may be sufficient sometimes to interpret the occurrence of highly related structures like the layer structures. Such structures have been discovered in numerous
systems, including the pure elements, intermetallic alloys, and metal/nonmetal compounds. For example, in
the alloy Au3Mg, a 2 l-layer stacking sequence has been
reported [92] and in silicon carbide, a 594 layer structure. [931With so many layers, a near-neighbor interaction
approach is unlikely to be fruitful. Eventually, of course,
a first principles calculation like the L M T O may become
possible.
IV.
METASTABILITY
which characterize phenomenologically the interactions

between various layers. Here, E(.e) and E(.i) are, respectively, the interaction between two equivalent layers such
as A and A, and two different layers, such as A and B,
and n denotes the separation of the two interacting layers. Even if only three parameters are considered, e~, e2,
and e3, representing second, third, and fourth adjacentlayer interactions, it is possible to analyze the relative
stability of all stacking sequences observed in the gen:
eral A3B-type systems. A stacking stability map constructed from such a calculation is shown in Figure 30.
Here, the interaction parameters are plotted as ratios
e3/le2] and eJle2 I, and the sequence of the possible layer
structures is depicted by the various areas on the map.
Which particular sequence is followed will be determined by a "path" chosen on the map (i.e., Q, P, R, S,
etc.) and this, in turn, depends on the chosen values of
the interlayer interaction parameters. In this way, ex-
I will have less to say about this subject, not because

it plays a lesser role in the phase diagram field, but because it has been addressed in two previous Campbell
lectures I94,951 and because it has grown so large that it
would be impossible to review even the major developments. It was Pol Duwez who emphasized so convincingly that rapid quenching of liquids can bring about
three possible effects: extensions of existing phases to
metastable composition ranges, new metastable phases,
and amorphous phase formation. Each of these fields has
grown rapidly. The most recent developments can perhaps be summarized as in Table VII. Whereas quenching from the liquid state had been the major topic only
a few years ago, solid-solid and vapor-solid reactions
now are the subject of numerous studies. The concepts
involved in metastability are most conveniently approached by trying to understand both the phase diagram
aspects and the underlying thermodynamics at the same
time, as in Figure 1. We can then see most clearly how
some minor shifts in free energy can alter the phase diagram to allow various possible metastable situations.
However, it becomes at once apparent that the major factor
may not be a relative shift in free energy curves, but
rather the elimination of phases, substitution of phases,
appearance of new phases, or merely supercooling or
(a)
(b)
e.
_t~7(e)
.
E ( i .)
[2]
Fig. 2 8 - - ( a ) AuCu3-type " T - m e s h " with "triangular ordering." (b) TiA13-type " R - m e s h " with "rectangular ordering." [Beckl88q
Table VI.
Layer Structures Involving A3B Compounds*
Period
Zhdanov Symbol
ABC Symbol
hc Symbol
Hexagonality (Pct)
Prototype
2
3
4
5
6
11
10
22
41
33
2211
52
3121
4111
44
71
3311
3212
221111
211211
63
5211
4221
3132
41111111
312111
21
AB
ABC
ABCB
ABCAB
ABCACB
ABCBCB
ABCABAC
ABCACAB
ABCABAB
ABCABACB
ABCABCAB
ABCACACB
ABCACBCB
ABCBCBCB
ABCBCBAB
ABCABCACB
ABCABCBCB
ABCABABCB
ABCACABCB
ABCABABAB
ABCACABAB
ABCBCACAB
h
c
hc
hhccc
hcc
hhhchc
hcccchc
hhcchhc
hhhhccc
hccc
hhcccccc
hhhcchcc
hhchcchc
hhhhhchc
hhhc
hccccchcc
hhhchcccc
hhchchccc
hhcchchcc
hhhhhhccc
hhhhcchhc
hhc
100
0
50
40
33
67
29
57
57
25
25
50
50
75
75
22
44
44
44
67
67
67
Cd3Mg (62)
Cu3mu (217)
Ni3Ti (13)
7
8
Co3V (2)
Pb3Ba (4)
*Pei and Massalskilgu
0.0
superheating o f existing p h a s e s , all b r o u g h t about b y kinetic considerations 9 H e n c e , the u n d e r s t a n d i n g o f kinetics often p r e d o m i n a t e s o v e r t h e r m o d y n a m i c s . E x a m p l e s

o f the c h a n g e s that can o c c u r in s i m p l e p h a s e d i a g r a m s
have been d i s c u s s e d b y P e r e p e z k o and B o e t t i n g e r [96]
a m o n g others, and F i g u r e 31 is b a s e d u p o n their work.
T h e ranges o f m e t a s t a b l e extensions, as well as the question o f w h e t h e r o r not the crystallization that m a y o c c u r
f r o m s u p e r c o o l e d liquids will i n v o l v e one p h a s e or several phases s i m u l t a n e o u s l y , is often a n s w e r e d b y the beh a v i o r o f the To t e m p e r a t u r e trends that have b e e n
o,v/
--
-0.5 -
?f
.......
~.
0.5
0.0
-0.5
- 1.0
--
31
I
1.0
-0.5
0.0
Fe
\ 1.0T /
0.5
1.0
19
29
2.5
Cu
Co
2.2T / / ~ ' = - " ' - ' - '
Ni
Cu
Ti
Ti--series
r
4
%%
.i
*~.
Cu
(b)
20A, A U G U S T 1989
31
V--series:
Fig. 29--Quasi-binary sequences of layer structures. [Pei and

MassalskW u]
1316--VOLUME
3.0
(a)
Ti
e2>O
el/le21
Ni
Ti
1Q
(a)
Ti
22_
11
. . . . . . . . .
Co
Fe
~e2<0
-1.5 -
. . . . . .
'~
-I.0 --
(b)
Fig. 30--Stacking stability maps. [Pei and MassalskiTM]
Table VII.
cations are, in fact, metastable diagrams which persist

in this form even with very slow cooling or lengthy annealing. The Fe-Fe3C phase diagram is a very old example of this. The work of Shingu et al. t~~176on the
Fe-, Co-, and Ni-based systems with carbon, involving
rapid solidification, refers to the more recent developments. Concepts of metastable diagrams involving rapid
liquid quenching date back to Pol Duwez's early work
on the Cu-Ag system.f941 Another example from that period
is the study of the Au-Sb alloys discussed by Giessen
and Willens, ~~ which is reproduced in Figure 32. Here,
the metastable phases not observed in the equilibrium
phase diagram have been revealed by liquid quenching.
Much has been written about glass formation and
amorphous phases in general. I shall not comment in detail on this here, but I would like to mention that the
fundamental question of whether or not a material that
appears to be amorphous on the basis of X-ray or electron diffraction patterns and a featureless appearance in
transmission electron microscopy (TEM) is actually
amorphous, or merely "nanocrystalline," has been addressed recently again by Chen and Spaepen. tl~ They
point out that the matter can be resolved satisfactorily
by additional careful thermocalorimetric work and its
interpretation. So, the problem addressed by Pol Duwez
in his Campbell lecture more than twenty years ago is
alive and well today.
Metastable Phases
Recent Developments:
(1) Some of the competing phases can be eliminated kinetically: we can change the phase diagram.
(2) Progress continues in the calculation of free energy
relationships at low temperatures: we can predict
metastability.
(3) Quenching can be done between different states:
(a) solid ~ solid
(b) liquid --~ solid
(c) vapor ~ solid
(4) Metastability can be obtained without quenching: solid
state amorphization, mechanical alloying, etc.
discussed in detail in the literature, t97,98,99~ The understanding of these trends again emphasizes the importance of thermodynamics at all temperatures. The
schematic trends shown in Figure l(a) illustrate how the
possible metastable ranges of a given phase are influenced by the To, T~,, or Tg trends* and how this influence
*For comments on the T,. trend, see the recent review by Johnson.t99j
can be projected on a phase diagram.
It is also helpful to remember that numerous phase
diagram systems used in everyday technological appli-
L
T
tx
L
""
"""
XB
XB
XB
(a)
f
f ~
",,S
s
.
XB
XB
(b)
XB
(c)
Fig. 3 1 - Metastable phase diagrams: (a) if a phase is eliminated; (b) if 31phase is excluded; and (c) if fl phase is excluded. [Perepezko and
Boettingerl~t]
VOLUME 20A, AUGUST 1 9 8 9 - - 1317
1200
' ,,,,
L~+L 2
4000
L=
I000
~)
800
6OO
3422 ~
.............................................................................
3~'o ...................................................................
IIL~::::::::;II
0
300o
(MP)
3000
2000
~. 4oo
200
,.,<,
//
/1/
"
100o
'"
2000
)84~ (MP)
Cu
!d,(~-I
....................................................................................................................................................................................................... - ~
I
10
I
20
I
30
I
I
I
40
50
60
atomic % W
I
70
I
80
I
90
lOOO
J
W
FCC
.IT.(.~ II
am+BCC
- 200
0
20
Au
40
60
Atomic F ~ e n t
80
I00
Sb
Antimony
I ='
BCC
Fig. 33--Recently assessed provisional phase diagram for the Cu-W

system based on a thermodynamic calculation. The ranges of rectastable phases produced by sputtering are shown below_ {Subramanian
and Laughlin cj~ and [Massalski and RizzoltcTq
(a)
17
o( -Au
AuSbz
Sb
(b)
Fig. 3 2 - - T h e system Au-Sb: (a) stable and metastable phase diagram
and (b) quenched-phase plot. [Giessen and Willens t~~
Interest in amorphous phases has led to numerous investigations into different alloy systems in search of such
phases and the techniques most useful to produce them.
A picture that has emerged confirms that amorphous
ranges will be obtained when crystallization can be suppressed kinetically and when the free energy of the liquid
state at low temperatures (i.e., the entbalpy AH~ iq) can
be lower in certain ranges of composition than that of at
least some of the crystalline phases that can compete with
the liquid. For example, in Figure 1, the free energy of
the liquid state at temperature T is lowest over quite a
wide range, provided the intermediate y phase is suppressed kinetically (i.e., removed from the metastable
phase diagram as in Figure l(c)). This usually requires
that the heat of formation (AHI) be negative in a given
alloy system. |991 A challenging situation occurs in systems where the opposite is the case, namely, where AHf
is positive. The contribution from the repulsive energy
between the alloying partners may be expected to be quite
large in systems such as Cu-W (AHI ~ 16 to 24 k J /
mole) or Pu-Ta (AHf --~ 1 1.3 k J / m o l e ) J l~ Here, the
phase diagrams show no mutual solid solubility or compound formation. Yet, the observed amorphous phase
formation and wide extensions of solid solubility are quite
substantial in both systems, tt~176 A calculated phase
diagram for the Cu-W system based on a simple thermodynamic model 1~~ is shown in Figure 33, together with
the indicated ranges of metastable phases (including an
amorphous range) that were recently observed in this

system following sputtering at room temperature, t'~
Massalski and Rizzo 0~ have suggested that for the purpose of interpretation, it is most convenient to regard the
sputtering process as a two-stage process. Almost instantaneously, sputtered atoms tend to be immobilized
as they are deposited from the vapor on the substrate.
The tendency here will be to form an amorphous state.
However, a good deal of subsequent adjustment is possible as sputtering continues. The likely free energy trends
in the Cu-W system at room temperature have been recently evaluated by Nastasi eta/. t'~ and are shown in
Figure 34(a). These authors have studied four codeposited Cu-W alloys and were the first to point out that the
initial amorphous state can decompose in a compositioninvariant manner (i.e., massively) or into equilibrium
structures, depending on the driving free energy and the
kinetic conditions. The driving force for the amorphous
bcc transformation is of the order of 10 to 15 k J /
mole, i.e., quite large, even at room temperature. A calculation by Miedema and Niessen I791shows that the driving force is likely to be smaller if elastic effects in the
crystalline phases are also taken into account
(Figure 34(b)). Since the amorphous state in the Cu-W
system is unstable at all compositions, how much of the
observed composition range will be amorphous, compared with possible massively formed crystalline or mixed
phases, will depend mostly on kinetic considerations.
Little information will be provided by the phase diagram
features. On the other hand, the T0principle may be applied to predict the possible relative ranges of the competing crystalline phases from the respective free energy
c u r v e s . [981 Similar effects are also observed in other systems with positive AHs, such as Fe-Ag, Cu-Mo, or PuTa. t'~ So, in these systems, phase diagrams and free
50
T:300
,~
Cu-W
40
2O
10
I
CU
20
40
atomic
60
W
I
80
W
(a)
W ~Cu
*30
"~ * 2 0
.10
/
BCC
I
|
,,, ,,
Fo:
0.5
cu
(b)
Fig. 34--Likely free energy curves near room temperature in the
Cu-W system: (a) [Nastasi, Saris, Hung, and Mayer,08q and
(b) [Miedema and Niessen179J].
energies are of some help, but kinetic considerations determine the ultimate result.
V.
ASSESSMENT
AND
DISSEMINATION
OF PHASE DIAGRAMS
To conclude my lecture, I must turn now to the basic

problem of phase diagrams: how accurate are they? We
all realize how the phase diagrams are determined. Very
rarely, a whole diagram is determined by one investigator. Even more rarely, an experimental determination,
involving more than one technique, is followed by a detailed thermodynamic modeling leaning on additionally
determined thermodynamic data. More typically, there
are various bits of information in the literature, some
metallurgical, some thermodynamical, and some theoretical. In each investigation, the purities of the materials
may not be the same, the techniques may be more or
less accurate, and many of the basic assumptions may

vary. It is also well known that different values of
thermodynamic quantities may account for the same diagram. It is not surprising, therefore, that many controversies exist about specific details in many phase diagrams
and that an assessment of a complex phase diagram may
present a very difficult task to a critical evaluator.
Attempts to produce assessed phase diagrams involving a review of the available literature dating back to the
1930's and the work of Hansen Ij~~ in Germany, including the later editions with Anderko ~H~Iin the United States
and supplements, 1~12,~3j stand out as early examples of
such important work. The major emphasis was on phase
boundary information, accompanied by some crystal
structure data. Metastable solubilities and phases were
not included (except, perhaps, for Fe-C) nor were any
thermodynamic data. Hansen made his own authoritative
decisions about phase nomenclatures and crystal structure designations, and probably many other features as
well, such as whether or not to use the centigrade scale,
atomic percentages, stoichiometric ratios, e t c . Nevertheless, these are probably the most widely used publications of evaluated binary phase diagrams. In addition to
these volumes, however, a large number of other publications have now appeared or are being produced; these
present partially evaluated binary diagrams displayed to
a varying degree of detail and scope, from a mere recording of phase boundaries to attempted calculated predictions of diagrams that have not yet been explored
experimentally. Such compilations, taken together, now
include thousands of systems.
During the 1970's, it became clear that a formal compilation and evaluation program which would update and
extend available compilations had been lacking; and until
very recently, there has never been a systematic and
comprehensive approach to ternary diagrams or other
multicomponent systems. The result has been an everincreasing gap between published and evaluated data. In
January of 1977, the National Bureau of Standards (now
renamed the National Institute of Standards and Technology) responded to the identified needs with a workshop, inviting people from nine countries to talk about
the need for phase diagram data, both alloy and ceramic,
and the applications of these data to science and engineering. This was followed, in February of 1978, after
a year of discussions and negotiations, by a formal
Memorandum of Agreement between the National Bureau
of Standards and the American Society for Metals (now
renamed ASM I N T E R N A T I O N A L ) to proceed with a
Phase Diagram Evaluation Program. I~laj
The first major step that affected plans for phase diagram compilation under the A S M / N B S program was the
recognition that with the mushrooming amount of phase
diagram information, an alphabetical, single-volume
scheme under the control of one author, or even several
authors, was no longer feasible. A single author might
be willing (and have time and resources) to review indepth perhaps 20 to 100 diagrams, but not thousands.
He or she may be familiar with systems based on a single
metal or a group of metals, but not familiar, or interested, in a completely different group. And, of course,
support for compilation and evaluation work may be
VOLUME 20A, A U G U S T 1 9 8 9 - - t 3 1 9
Alloy PhaseDiagram
International
Commission
I ASMAlloy lPhaseDiagram
Committee
I Funding
Activity
ASM/NBS
ProgramManagement
J,
Contractsand
Appointmentsto
EvaluateMetalSystems
Category Editors
Contributing Editors
Reviewers
PrintedProducts
ComputerDatabases
Periodicals
Bibliographic
ReferenceWorks
Numerical
Monographs
Graphics
Fig. 35--Interactions involved in producing and publishing phase diagram assessments.
ASM
INTERNATIONAL
National Bureau
of Standards
anadizm Phase Diagram

Research Association
Max Planck Institute f/Jr

Metallforschung, Stuttgart
The Indian Institute

of Metals
" Alloy Phase Diagram "
International Commission
(
eutsc e Gesellschaft "~
~ . ~ e t a l l k ~
CODATA
Groupe de
Thermodynamique et
)ia~rammes de Phases
Editor in Chief
Binary Systems
Editor in Chief
Ternary and Higher
Order Systems
Japanese Committee
for Alloy Phase
Diagrams
_.
Fig. 36--Binary phase diagram assessments in the framework of international cooperation.

available for systems based on a particular metal, but not

all systems alphabetically.
Accordingly, the best solution was to divide the systems into suitable categories and to arrange for each category to be compiled and evaluated under the guidance
and responsibility of a specific Category Edit+r, each for
a given finite set of systems. Later, Contributing Editors,
who would evaluate only a few systems of specific interest to them, were added to this approach. It was also
soon recognized that phase diagram evaluation programs
are an international task, because only through international cooperation can all resources be brought together
and a duplication of effort avoided. The present situation
is best summarized with reference to Figures 35 and 36.
Further details are available in the literature. IHS-N81
Figure 35 illustrates the various complicated interactions
needed to produce the final assessments. While it can
be seen that numerous people are involved in various
activities, the most important are the category and
contributing editors and the reviewers because their
professional backgrotmd and experience and their enthusiastic commitment toward performing the needed phase
diagram evaluations have made the continuing progress
possible. The international nature of the program is illustrated in Figure 36. We now have in existence an Alloy
Phase Diagram International Commission (APDIC),
whose main tasks are to coordinate efforts, maintain
standards, and prevent duplication. I have chosen to report on these developments in this lecture because, ultimately, only through the efforts of all those who have
the need to use phase diagrams and who realize that the
accuracy of the available information has a direct bearing on their own work, shall we be able to maintain standards and the necessary momentum. So, these efforts
will depend on the good will and interest of all of you
present in this room today and numerous others
worldwide.
ACKNOWLEDGMENTS
I am most grateful to a number of my colleagues
who read this manuscript prior to publication and contributed valuable comments or who have made available
some results or graphs prior to publication (in particular,
Dr. H. Rizzo, Dr. William C. Johnson, Professor
T. Nishizawa and Professor D.E. Laughlin). The figures
and tables were produced by computer graphics with
the help of Mr. G. Pierini. Much of my own research
related to phase diagrams and reported here has been
over the years largely supported by various grants from
the National Science Foundation, Washington, DC, and
these have made possible m y long-term interest in this
field.
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The 1988 Campbell Memorial Lecture

Phase Diagrams in Materials Science

The Edward DeMille Campbell Memorial Lecture was established

THIS lecture commemorates the name of Edward

understanding. This interdependence is not new. In

Fig. 1 - - P h a s e diagrams and free energy. (a) A schematic binary phase

ferent applications. For example, it can be concluded that

While it is not appropriate to review here all of the

G = SAGA + XBGB + ~XAXB + RT(XA lnXA + XB InXB)

RT(XA lnXA + XB lnXB)

e =eAB -- ~ (eAA + eBB)

.QL (kJ mo1-1)

A consequence of this set of relationships is the Gibbs

The Phase Rule*

Thermodynamical Condition for Equilibrium

GL--~X~)~AH~p --= m o l a r enthalpy o f first precipitation o f / 3 from

A or B elements to the compound will neither lower the

depended on visual rendering of phase diagrams, usually

portions, and other interpolated features. The various

Fig. 7 - - C h e m i c a l and coherent spinodal lines. [Laughlin and Soffa1291]

graphically) becomes stable and the four phases become

E. Coherent Equilibrium and "Coherent

each new phase first appears, but also the compositions

multiphase mixtures or during precipitation, particularly

/ _2.5%N~ LID SOLUTION

where G i is the free energy of the i t~ phase in an

Numerous problems and questions have been and are

Tsothermal section-Vertical section

calculation for semiconductors. [Tokunaga, Ohtani, Ishida, and Nishizawa148q

compete in phase diagrams are often very small indeed,

Along with the progress achieved in the measurements

Phase diagrams via interpolation. [Okamoto and MassalskP 491]

Fig. 18--The driving free energy for the massive transformations in

phase diagram Au-Nd. [Okamoto and

measurements have not yet been done or are particularly

Fig. 1 7 - - C o m p a r i s o n o f c a l c u l a t e d and e x p e r i m e n t a l p h a s e boundaries in the C u - G a system. [Subramanian, Laughlin, and M a s s a l s k i tS~

prediction of phase stability of alloys and compounds in

phase diagram of a binary alloy starting first with the

Phase Stability Calculations*

Calculate self-consistent atomic potentials of components.

Result: total energy

Possible Number of Systems

n = number of elements (say 90)

Table V. Recent Theoretical Calculations

Miedema et al. [561

Mott and Jones t681

Williams et al. tS~l

The stability ranges and various properties of the phases

(a phases), having the fcc structure found in the noble

intermediate phases, as if a "rigid band" behavior related

Fig. 1 9 - - T y p i c a l alloy phase diagram characteristic of the noble metals.

to explain the stability of these phases. The most likely

~" phases as shown in Figure 22(a), Massalski and

N;(E)dE - k E~ Nv(E)dE = 2oo cal/mole

i.e. 0.1% of total electronic

1310-- VOLUME 20A, AUGUST 1989

holding the key role in determining the relative stability

priate solutions of the Schr6dinger equation. For pure

C. First Principles Calculations

Cu 0.2 0.4 0.6 0.8 Au

Ag 0.z 0.4 0.6 0-8Au

VOLUME 20A, AUGUST 1 9 8 9 - - 1311

phases are favored as observed, and the miscibility gap

Fig. 2 4 - - " F i r s t principles" phase diagram calculation. [Hafner t63J]