Phase Transformations in Metals and Alloys PDF

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PHASE TRANSFORMATIONS IN
Annu. Rev. Mater. Sci. 1973.3:327-362. Downloaded from arjournals.annualreviews.org
METALS AND ALLOYS 8546

by HARVARD UNIVERSITY on 11/23/08. For personal use only.
Glyn Meyrick and Gordon W. Powell

Departmentof Metallurgical Engineering, The OhioState University, Columbus,Ohio
INTRODUCTION
Understanding a phase transformation involves an appreciation of the reasons

for its occurrence and of the modeor modesby which it takes place. The former
will not be explored herein beyond noting that a system can spontaneously
undergo a change in phase (or phases) if by so doing its free energy is reduced.
Provided a reduction in free energy ensues, the product of the transition need not
be that pertaining to the equilibrium state. A total change mayyield directly the
equilibrium state or traverse a path composedof several tranformations involv-
ing metastable phases. This, combinedwith the fact that a given change can be
accomplished by more than one kinetic mechanism generating modal competi-
tion, endows the study of phase transformations and their consequences with the
complexities that render it so intriguing. Phase transitions have received exten-
sive investigation because of their inherent fascination and because they play a
particularly important role in property control for material applications.
As can be seen from someof the more recent surveys of the field (1-3) it
customary to group together changes that exhibit commoncharacteristics in an
effort to classify phase transformations in a systematic manner. Criteria involved
in classification are predominantly of morphological character but also include,
or imply, mechanistic processes. This process has led to the establishment of
accepted group names: 1. continuous precipitation, 2. massive transformations,
3. discontinuous precipitation, 4. martensitic transformations, 5. bainitic trans-
formations, 6. order-disorder transformations, and 7. spinodal decomposition.
Because of an initial restriction on the length of this review, order-disorder
transformations and spinodal decomposition will not be considered here, but
they have been discussed by Wayman(4) in a pi’evious volumeof this series.
Continuous precipitation is characterized by the formation of grain boundary
and intragranular particles of the newphase, which generally has a structure and
327
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328 MEYRICK ¯ POWELL
composition different from that of the metastable matrix. The growth of the new
phase is controlled by long range diffusion through the matrix, whose average
composition changes continuously as the reaction proceeds. The reaction at the
interface between the parent and product phases is presumed to be relatively
fast.
If the new phase forms by the massive mode, it has the same composition as
the parent phase and the reaction is accomplished by the rapid motion of a high
energy, incoherent boundary. Thus this solid state reaction does not involve long
range diffusion and the transfer of atoms from the parent to the product phase
is assumed to be effected by the uncoordinated, random jumps of individual

atoms across the interphase boundary. Although Phillips (5) was apparently the
first investigator to recognize this modeof transformation as a unique type of
solid state reaction, the term massive was first applied by Greninger (6). It is
appropriate term in the sense that it is descriptive of the relatively large

morphological units which in some cases form by this mode of transformation.
The discontinuous modeof transformation results in the formation of a two-
phase mixture at an advancing, incoherent boundary. The atom transport and
atom rearrangement required to produce the two-phase mixture are assumed to
take place in the advancing boundaryand also, if volumediffusion is significant,
within a region immediately adjacent to the advancing boundary. The bulk of
the metastable matrix remains essentially unchanged until traversed by the
interface. Generally, the compositions and crystal structures of the two phases
are different from that of the metastable matrix. The two phases are often
arranged in the form of a lamellar aggregate.
The martensitic mode of transformation yields platelets of an oftentimes
transitional phase by a displacive reaction which is diffusionless, produces
surface relief effects, and is reversible in somealloy systems (7). In addition,
definite crystallographic relationships exist between the product and parent
phases, and the physical plane of the martensitic platelet is usually parallel to an
irrational lattice plane (habit plane) of the metastable matrix. Since the formula-
tion of th~ phenomenological theory of displacive reactions by Wechsler,
Lieberman & Read (8) and Bowles & Mackenzie (9), much of the research
been concerned with the crystallographic and geometrical aspects (lattice rela-
tionships, habit plane, shape deformation, and inhomogeneous deformation
within the martensite) of martensitic transformations.
The bainitic modeof transformation is the subject of considerable controversy
as demonstrated quite clearly by a recent debate on this reaction (10). Somesolid
state reactions which occur in ferrous and nonferrous alloys and whose products
have distinctively different morphologies have been labeled bainitic. In the case
of hypoeutectoid steels, lower bainite has some of the characteristics (lattice
relationships, surface relief, inhomogeneoussubstructure) of martensite, but the
slow edgewise growth of the platelets of bainite is controlled by the rate of
diffusion of carbon in the austenite matrix.
Whereas a classification scheme based upon clearly distinguishable modes of
transformation has obvious merits, it can also be disadvantageous if adhered to
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PHASE TRANSFORMATIONSIN METALS AND ALLOYS 329
too rigidly. It is to be emphasizedthat a phase transition can involve a structural

change, a compositional change, or both. All of these can, in principle, be
accomplished by diffusion processes, while part can be achieved by displaeive
processes. Both processes could be operative in a given transformation and might
or might not be practically separable. Thus, although transformations exist that,
by commonagreement, belong within a particular group, others exhibit charac-
teristics of several groups. It is moreprofitable to regard this main classification
as establishing general guidelines rather than providing a series of separate
compartments into which all transformations can be unequivocally placed.
The objective of this review is primarily to summarize on the basis of
experimental observations the current knowledge of the morphological and

growth characteristics of the various modes of transformation. It does not
consider in any great detail mathematical models of these reactions. Each of the
various modes of transformation will be considered under one of three broad

groups of solid state reactions: 1. diffusional transformations, 2. displacive
transformations, and 3. hybrid (mixed mode) transformations.
DIFFUSIONAL TRANSFORMATIONS
Massive Transformations
As noted in the introduction, a massive transformation is accomplished by the
rapid motion of a high energy, incoherent boundary which converts the parent
phase into a more stable phase of the same composition. Any nonmartensitic
polymorphictransformation in a pure metal is obviously a degenerate or limiting
case of a massive transformation. Thus Owen& Gilbert (11) suggested that the
"r-to-a transformation which occurs in pure iron at cooling rates less than
5500°C/sec is a massive reaction. These observations were made on bulk
specimens. Differences are to be expected for microscopic specimens; for
example, the a-to--/transformation in iron whiskers exhibits characteristics of a
martensitic transformation and is well described by the phenomenologicaltheory
(12). Bibby & Parr (13), using iron containing less than 0.0017% C,
concluded that the transformation at cooling rates less than 30,000°C/sec is
massive. At higher cooling rates the "r-to-a transformation is martensitic. Typical
massive microstructures obtained by cooling pure iron (0.001%C) at slow rates
are shownin Figure 1; in general the grain size decreases with an increase in the
cooling rate. This modeof transformation does not 15roduce surface tilts (13-15),
a fact consistent with the concept that the boundary between the transformed
and untransformed region is displaced by the random, noncooperative move-
ment of the atoms at the boundary; Transmission electron microscopy has shown
that the internal structure of the massiveferrite grains consists of a randomarray
of dislocations and that neighboring massive grains are separated by high angle
boundaries (14, 15) (Figure 2). The dislocations maybe the result of transforma-
tion-lnduced stresses and quenching stresses.
The motion of the austenite-ferrlte boundary in pure iron at undercoolings on
the order of 25-50°C has been investigated by Eichen & Spretnak 06) and
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330 MEYRICK & POWELL

Figure I Microstructure of high punty iron quenched at approximately(a) 800"C/sec and

(b) 4000"C/sec. X 300.
Figure 2 Random dislocations and high angle boundary in iron quenched at 3300"Usec.
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Bharucha et al (17) by the use of thermionic emission microscopy. The geometry

and motion of the austenite (light)-ferrite (dark) interface are shownin Figure
3; the elapsed time between the two photographs is 15/16 sec. The a-v interface
is highly irregular and faceted, and it moves in a definitely discontinuous
manner. That is, segments of the interface may remain stationary for a fraction
of a second and then undergo sudden displacements. Discontinuous interface
motion is not unique to the massive transformation in pure iron.
In the case of alloys, the massive transformation in the Cu-Gasystem has been
studied quite thoroughly; investigations of the massive transformation in Cu-Zn
alloys have also yielded some significant results. The discussion of the Cu-Ga
and Cu-Zn alloys considers in order the following kinetic, morphological, and
crystallographic features: nucleation site, rate and mechanism of interface
motion, lattice relationships between the massive phase and its parent, structure
of the massive boundaries, and internal structure of the massive phase.

The high temperature fl (bcc) phase in a Cu- 37 at.% Zn alloy can be retained
to room temperature by rapid quenching, but during the quench some of the fl
phase does transform to Widmanstatten alpha phase a w and also to massive
alpha am" Both the aw and otm phases nucleate at the fl-fl grain boundaries. The
results of rapid up-quenching experiments have shown that the aw-fl boundaries
which may be semicoherent are not suitable sites for the formation of am phase
(18). Furthermore, whenthis alloy is equilibrated at a temperature such as 840°C
in the (a + /3) phase field and then quenched, the a,~ phase again nucleates
preferentially at fl-fl grain boundaries. Nucleation of a,~ was not observed at the
aeq - fleq boundaries; such boundaries should be at least semicoherent and thus
lack the mobility required for the massive transformation. Consequently, it may
be concluded that boundaries with disordered atom arrangements are favorable
sites for the nucleation of a massive phase.
The growth rate of the massive phase amin the fl Cu-Zn alloys is approximat-
ely 1 cm/sec (18, 19), which is orders of magnitudegreater than that associated
with transformations controlled by long range volume diffusion. At such high
growth rates, the massive phase must have the same composition as the parent
phase. The microprobe scans of the ~,~ and/3 phases in a rapidly quenched Cu
-38.5 at.% Zn alloy obtained by Massalski et al (20) are convincing demonstra-
tions of this fact. The morphological development of the a,~ phase in a quenched
Cu-37 at.% Zn alloy is shown in Figure 4. The am-fl surface enclosing any
given morphological unit of a,~ contains many facets. Transmission electron
micrographs obtained by Hawbolt & Massalski (18) of the faceted a,,-/3
interfaces show that interfaces contain steps or ledges, the smallest ~ 100/~ in
height (Figure 5). Ledges 6-30/~ in height have been observed on the faceted
~’,n-fl interfaces in /3 (bcc) Cu-Gaalloys (21). The existence of ledges on
faceted interfaces is consistent with the theory of growth proposed by Aaronson
(22). According to this theory, growth perpendicular to the faceted interface
occurs by the lateral motion of the ledges across the interface which is assumed
to have a misfit dislocation structure that renders it relatively immobile. The
highly mobile ledges, on the other hand, are considered to have a disordered
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332 MEYRICK L POWELL
.
Figure 3 Austenite (light)-to-ferrite (dark) transformation in high purity iron. Elapsed

time is 15/16 sec. Magnification is approximately X 100.
Figure 4 Morphology of the a, phase in a Cu-37.8 at.% Zn alloy.
structure. Growth of the ,{ phase in /3 Cu-Ga alloys by the ledge mechanism has
been observed by Kittl & Massalski (21) using hot-stage microscopy.
The a, (fcc) and /? (fcc) phases abutting one another across a faceted interface
in Cu-Zn alloys are oriented at random with respect to one another (18). The
faceted interfaces do not correspond to any unique habit plane; attempts to
observe misfit dislocation arrays at these interfaces were unsuccessful. However,
in the case of the /? (bcc) + 3, (hcp) reaction in /3 Cu-Ga alloys, crystallography
can play a role in the transformation. The J,,, grains often consist of two twin-
related subgrains and at least one of the twin-related regions is bounded in part
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by facets. Thetraces of these facets are consistently parallel to the (0001) basal
plane of the ~’m phase and growth takes place by the rapid movementof ledges
along facets (Figure 6). The volume change associated with the transformation
induces slip ahead of the advancing interface. If the parent and product phases
are related crystallographieally to one another according to Burger’s lattice
relationships (110)B II (0001)~mand [11~]BII [1 l~0]~m,then a (110} plane in the
/3 matrix is parallel to the facets on the ~,n morphologicalunits. The {110}plane
is a potential slip plane of the bcc lattice; in fact, slip in the/3 phase parallel to
the faceted sections of the fl-~,, interface has been observed. Slip in the /3
matrix impedes the motion of the advancing interface and, according to Kittl &
Massalski (21), provides a mechanism for the formation of ledges. When

unimpeded sections of the interface contact a (110)~ plane on which slip
taking place, semicoherent /3-~m interfaces are formed and produce the
interface geometry shown in Figure 7. The precise mechanism by which the

twinned ~munits form is unknown. The lattice relationships between the twin
subgrain and the /3 matrix are undoubtedly established during the nucleation
stage of the transformation.
The rapid growth rate of a massive phase and the ability on occasions of the
massive phase to penetrate a grain boundary and grow into an adjoining grain
are indicative of the random, incoherent structure of the boundary between the
massive and parent phases. Somedirect experimental evidence supporting this
conclusion has been obtained by Perkins & Massalski (23) who studied the fl-
to-~,n transformation in equilibrated (~ + ~’) Cu-Ga-Gealloys. The massive
transformation occurred in the quenched alloys by motion of certain prior fl-~
boundaries; the other /3-~ boundaries were inactive and remained stationary.
Because small particles of untransformed fl phase were present in the quenched
alloys, it was established by transmission electron microscopythat (a) no unique
crystallographic relationships exist betweenthe fl and ~ phases across either the
active (fl-~m) or the inactive (B-~) boundaries, but (b) the habit of the inactive
(,8-~) boundaries corresponds to a low index plane such as the basal or prism
planes, whereas the habit of the active prior (/3-~) boundaries is in general
irrational. Thus if one thinks of the/3-~ boundaries in terms of regions of good
fit (coincidence boundary) connected by regions of bad fit, the irrational and
active/3-~ boundaries should have a higher density of the more mobile regions
of bad fit in comparisonwith the low index, inactive/3-~" boundaries.
The internal structure of the ~,n phase formedby the fl-to-~; m massive reaction
in/3 Cu-Ga(24) and (fl + ~) Cu-Ga-Ge(23) alloys consists of an irthomogeneous
distribution of stacking faults and dislocations on the basal plane of the hcp
structure. The stacking faults maybe either growth faults or deformation faults
produced by the transformation stresses. The massive phase produced by the/3-
to-a m transformation in a Cu- 37.8 at.% Zn alloy (18) also has n i n_homogeneous
internal structure composedof dislocations and possibly some stacking faults.
Thus, with the exception of the stacking faults, the internal structure of the alloy
massive phases am and ~mis not unlike that of its counterpart in pure iron.
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334 MEYRICK ~r POWELL

Figure 5 (a) Microsteps, 100 8, in height, on am# boundary. (b) Macrosteps, on a,-P
boundary.
Figure 6 Ledge growth of the 8, phase in a Cu-22.8 at.%Ga alloy.
/ I
c__c_
Figure 7 Ledge growth of a twinned 8, crystal accomodated by slip in the /3 matrix (after
Kittl & Massalski, 21).
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Discontinuous Precipitation
Discontinuous precipitation is the formation of a two-phase product from a
single metastable phase, the product phases normally being dispersed in the form
of alternating, parallel lamellae. In the simplest case the metastable phase is a
supersaturated terminal solid solution (ass) which transforms below the solvus
temperature to equilibrium alpha, aeq, plus a second phase //, which has a
structure and composition different from that of the O~eq with which it coexists.
In the case of Fe-Zn alloys (25) discontinuous precipitation occurs at tempera-
tures below approximately 0.93 of the absolute solvus temperature and, for an
A1- 17 wt%Ag alloy (26), the reaction occurs below 0.87 of the absolute solvus
temperature; at higher temperatures continuous precipitation occurs, but, over a
limited temperature range, the two modes of transformation may compete with
one another. The decomposition of Fe-C austenite to pearlite is a more complex

discontinuous reaction because the parent and product phases all differ in
composition and structure. The massive transformation might be regarded as a
limiting form of discontinuous precipitation in which only a lattice transforma-
tion occurs, whereas the atom transport required for the precipitation of the
other phase is prevented by the external constraints, e.g. cooling rate.
In 1953 Smith (27) set forth a theory of discontinuous precipitation which has
served as the basis for manyof the subsequent theoretical treatments of this
reaction. Smith stated that the cells, which nucleate at grain boundaries, grow
preferentially into one of the grains which abut the grain boundary by the
motion of a "disordered, incoherent" interface. The composition changes
required to produce the lamellar product are brought about by lateral diffusion
along this interface. Futhermore, the disordered, incoherent interface bounding
the growing cell is actually continuous with the original grain boundary at which
nucleation of the cell occurred and which has bulged into the grain under the
influence of the driving force for the transformation. Consequently, as pointed
out by Smith, the predominant phase in the cellular product is continuous with
(i.e. has the same orientation as) the grain awayfrom which the growth front
moving. It was anticipated that rational crystallographic relationships would
exist between adjacent lamellae (a and B), thereby minimizing the proportion
the driving force consumed by the formation of new interfaces. Subsequent
research on discontinuous transformations has not altered in any significant way
Smith’s description of this reaction.
The recent research on this mode of transformation has been concerned with
the nucleation stage of the transformation, the mechanismfor the development
of cooperative growth, the mechanism for changing the spacing between
lamellae, and, of course, development of more rigorous mathematical models of
cell growth. This discussion of the discontinuous mode of transformation
considers the following topics: nucleation of lamellae and the evolution of
cooperative growth, mechanismsfor changing lamellae spacing, growth kinetics,
and nonequilibrium transformation products.
The cellular reaction in bicrystals of a Pb-7 at.% Sn alloy has been subject to
thorough study by Tu & Turnbull (28-30). The bicrystals contained a [001]pb
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symmetric tilt boundary, the misorientation 0 about the [001]~,b ranging from
7-37 °. The appearance of the tin-rich platelets at an early stage of the
transformation is shown in Figure 8 and the morphologyof well-developed cells
is shown in Figure 9. The crystallographic relationships between the tin-rich
lamellae and the solute-depleted lead are (010)sn [[ (11 l)p b and [001Isn 1[ [110]pb,
the habit plane of the lamellae being (111}pb. The planes and directions involved
in these relationships are the most densely packed planes and directions of the
two crystal structures. Note that the tilt boundaryin Figure 8 is not straight, but
has becomebowedor deflected in the immediate vicinity of the tin-rich lamellae
at the boundary. Futhermore, the lamellae lie within the grain on the left. Thus,
of the two broad faces which bound each platelet, one is a low energy interface
and the other, which separates each platelet from the grain on the right, is
presumably a high energy, incoherent boundary because the platelets are not
related in the crystallographic sense to this grain.
On the basis of these observations Tu and Turnbull have proposed that the
development of a cell takes place in the manner shown schematically in Figure
10. The arrows in Figure 10a indicate in each grain the (110) directions, which
also are the traces of the (111) habit planes in the [001] bicrystals. Whena
platelet lying within the al grain forms at the grain boundary, the grain
boundary must be deformed locally to satisfy the habit plane requirement of the
platelet (Figure 10b). Subsequently the high energy, incoherent/~-a 2 interface is
replaced by a lower energy fl-al interface due to displacement of the. grain
boundary as shown in Figure 10c. Displacement of the grain boundary serves not
only to embedthe platelet wholly in the o/I grain but also to movea segment of
the grain boundary into an orientation favorable for the formation of a second
platelet lying parallel to the first (Figure 10af). Thusthe pattern of cooperative
growth is established by a repetition of this process.
As noted earlier, Smith’s (27) model of discontinuous precipitation requires
that the lamellae within a cell be related crystallographically to the grain away
from which the cell is growing, and the mechanism depicted in Figure 10 is
consistent with this requirement. Tu & Turnbull (29) and Liu & Aaronson (31)
have observed that cells do not form when the misorientation ® about the
[001h,b axis of the bicrystals is smaller than 15°. Here again, this observation is
consistent with Smith’s model in that low angle tilt boundaries possess neither
the structure nor the mobility to support cellular growth.
Although the mechanismillustrated in Figure 10 for cooperative growth is
extremely attractive because of its relative simplicity, the operation of this
mechanism in alloy systems other than Pb-Sn has not been reported in the ¯
literature. Somerecent research by Fournelle &Clark (32) on cellular precipita-
tion in a Cu-9.5 at.% In alloy has yielded results which have led to the
formulation of a generalized theory and criterion for the development of
cooperative growth. In this alloy the discontinuous reaction is preceded by the
formation of well-developed grain boundary allotriomorphs of the 8 phase
(CuaIn4) but develops subsequently from the allotriomorphs. The sequence
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PHASE TRANSFORMATIONS IN METALS AND ALLOYS 337

Figure 8 Early stage of cellular growth Figure 9 Fully-developed cells in a Pb-

in a bicrystal of a Pb-7 at.%Sn alloy. 7 at.%Sn alloy.
Figure 10 Development of cooperative growth by the Tu-Turnbull mechanism (after Tu

& Turnbull, 28).
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events producing cooperative growth is beautifully illustrated by the transmis-

sion electron micrographs in Figure 11 and is illustrated schematically in Figure
12. A grain boundary pinned at some points by allotriomorphs bows out between
the particles. As the grain boundary moves, it leaves behind solute-depleted tt
phase, the solute having diffused along the bowedboundary to an allotriomorph.
Consequently the allotriomorphs becomeextended parallel to the direction of
motion of the grain boundary and the pattern of cooperative growth is thereby
established. The initial driving force for grain boundary migration is derived
from such factors as the local curvature of the grain boundary and the relative
perfection of the abutting grains (strain-induced grain boundary migration).
However, once the solute-depleted ~t forms behind the advancing interface, the
driving force for boundary migration is derived primarily from the difference of
the chemical free energy between the supersaturated a phase and the solute-
depleted a phase. The Fournelle-Clark mechanism for the development of

cooperative growth provides an explanation for the fact that continuous precip-
itation occurs at temperatures above approximately 0.8-0.9 of the absolute
solvus temperature, whereas the cellular reaction is favored below this tempera-
ture. In the higher temperature range the chemical free energy is simply not of
sufficient magnitude to bow out the boundary between the allotriomorphs.
Althoughthe austenite-to-pearlite transformation in steel has been the subject
of almost innumerable investigations, the mechanism(s) by which cooperative
growth is established remains unknown. Hull & Mehl (33) proposed that the
sidewise growth of a pearlite colony occurs by the successive nucleation of ferrite
and cementite, the initial nucleus being a platelet of cementite. After the
formation of the initial platelet of cementite, the platelets of ferrite nucleate in
the adjacent carbon-depleted austenite, etc. However, subsequent research
(34-36) has demonstrated quite clearly that a pearlite colony can originate from
either a ferrite (hypoeuteetoid steel) or cementite (hypereutectoid steel) nucleus
and, furthermore, sidewise growth by successive nucleation of the lamellae has
not been confirmed experimentally. The Fournelle-Clark mechanism (32) de-
scribed above seems capable of being applied under some circumstances directly
to the pearlite reaction. Consider, for example, a ferrite allotriomorph (Figure
13a) allowed to form isothermally in the (y + ct) phase field. As shown
experimentally by Hillert (37) and depicted schematically in Figure 13b, pearlite
forms at the upper ~t-y boundary during a moderately fast quench from the
temperature at which the allotriomorph formed. In the initial stages of the
quench; particles of cementite nucleate at the tt-y interface which may have
moved a small amount, thereby producing a local enrichment of the carbon
content within and/or in the immediate vicinity of the boundary. Continued
cooling produces the driving force necessary to bow out the a-y boundary
between the cementite particles (Figure 13d). Subsequent growth of the cementite
particles occurs as shown in Figure 12. In agreement with experiment, the
pearlitic ferrite is continuous with the ferrite allotriomorph and thus has the same
crystallographic orientation. It is not clear, however, as to whether or not the
cementite lamellae should have a specific crystallographic orientation.
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PHASE TRANSFORMATIONS IN METALS A N D ALLOYS 339

Figure 11 Development of cellular growth from allotriomorphs in a Cu- 9.5 at.%In alloy.
Figure 12
%
b
C d
-
a'
8
L Twins
a
e
I a'
Development of cooperative growth by the Fournelle-Clark mechanism (after

Fournelle & Clark, 32).
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340 MEYRICK,~ POWELL
According to Zener’s theory (38) of the cellular reaction, the intedamellar

-l
spacing
. S should vary inversely with the amount of undercooling, i.e. S a AT
The results of some experimental studies (40, 41) have confirmed this relation-
ship; however, in the case of Fe-Zn alloys Speich (25) found that the interlamel-
lar spacing did not vary linearly with AT-l , a result rationalized qualitatively by
a modification of Cahn’s theory of cellular growth (39). A temperature change
during the growth of a cell must be accompaniedby a change in the interlamellar
spacing which can take place by one of the following mechanisms: branching,
nucleation of new lamellae at the advancing cell boundary, or separation of the
cell boundary from the tips of the lamellae. The first two mechanismsdecrease
the interlamellar spacing whereas the last increases the spacing.

Figure 14 is a schematic summary of the means whereby changes in the
spacing between the cementite lamellae in pearlite have been observed to occur.
In the case of pearlite the spacing is decreased by the branching mechanism

(Figure 14a, b, c). Onecan regard the sequence of events illustrated in this figure
as a variant of the Fournelle-Clark mechanism. When the temperature is
decreased, the ferrite-austenite boundary adjacent to the cementite lamellae
bows out into the austenite, the carbon atoms subsequently collecting in and
precipitating on the displaced boundary. The driving force to bulge the boundary
into the austenite adjacent to the cementite lamellae arises from the anticipated
lower carbon content of this austenite and hence a higher TO temperature. If the
, temperature is suddenly raised during the growth of a pearlite colony, the
interlamellar spacing car~ be increased by replacive motion of the ferrite-
austenite interface as shownin Figure 14d; this process also may involve partial
dissolution of the eementite at the tip of the lamella. The interlamellar spacing
may be decreased by nucleation of new lamellae at the advancing interface, as
can be seen in Figure 11 for the Cu - 9.5 at.% In alloy. This mechanismalso has
been observed to operate in Pb-Sn alloys (29). In the case of pearlite, Sundquist
(42) has stated "that interlamellar spacings observed experimentally are those
the verge of instability with respect to the formation of a new lamella of Fe3 C
at the middle of a ferrite lamella-austenite interface."
Data for the cellular growth rate ~ can often be fitted to an equation of the
form
wherein ATis the undercooling and Q is the activation energy for diffusion. The
growth rate is low at high temperatures (small AT) because the interlamellar
spacing is large and the driving force for the reaction is small, and is also low at
low temperatures because the diffusion rate is slow; thus the growth rate attains
a maximum value at some intermediate temperature. On the basis of the simple
models which yield an equation of this form, a value of n = 2 is associated with
volume-diffusion-controlled growth (38), whereas a value of n = 3 is appropriate
for interface-diffusion-controlled growth; consequently the corresponding activa-
tion energies are those for volumeand grain boundary diffusion respectively. The
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growth rate for the cellular reaction in the austenitic Fe-30Ni-6Ti alloy studied
by Speich (41)
800’~
G(mm/min) = 281 (982 - T°C) 2 -39’
exp(
Although this equation has the form associated with volume-diffusion-controlled

growth, the activation energy of 39,800 cal/mol is considerably smaller than that
for the diffusion of nickel in iron (67,500 cal/mol). Thus an unambiguous
physical interpretation of Equation 2 is not possible. If it is assumedthat the
growth of pearlite occurs by diffusion of carbon along the pearlite-austenite
interface and the effects of capillarity and imperfect carbon segregation are taken
into account, the cellular growth rate should be given by an equation of the same
form as Equation 1 with n ---- 3 (42). Whendata for high purity Fe-C alloys are
fitted to this equation the activation energy is computedto be 45,700 cal/mol,
muchlarger than that expected for interface diffusion. Sundquist has attributed
the high activation energy to an impurity effect.
To derive a growth rate equation which in the final form does not contain
explicitly the interlamellar spacing, it is necessary to employ a priori an
extremum principle. For example, Zener assumed that the observed spacing is
that which maximizes the growth rate. Other criteria which have been used are
maximumrate of entropy production (43) and maximumrate of decrease in free
energy (39). At the present time there is no evidence which suggests that one
these criteria is superior to the others.
The products of a cellular reaction may not have the compositions correspond-
ing to the equilibrium state. Thus, in the case of the eutectoid reaction
(/~ --> a + T) in a 94%Cu-6%Be alloy, the a phase is initially supersaturated
with respect to beryllium, but with continued aging the supersaturation is
relieved by diffusion of the excess beryllium atoms to the T phase (44). A similar
situation has been found by Speich (25) in Fe-Zn alloys. The a phase of the
cellular product is supersaturated with respect to zinc, the extent of the deviation
from equilibrium increasing with decreasing reaction temperature and also with
increasing zinc content of the alloy (Figure 15). Here again, the supersaturation
of the ct phase is relieved by diffusion of zinc to the T lamellae.
One of the phases in the lamellar product may be a metastable phase. This is
apparently the case for the cellular reaction in an austenitic Fe-30Ni-6Ti alloy.
At temperatures in the range of 700-900°C, equilibrium requires a two-phase
mixture of austenite plus (Fe, Ni)2Ti. However, the initial cellular product
consists of austenite plus Ni3 Ti lamellae (3’.~ --~ 7B + Ni3 Ti). The equilibrium
state is achieved subsequently by means of a second cellular reaction
+Ni3Ti ~ "/c + (Fe, Ni)2Ti ]. In some instances, however, the two reactions,
Y,~ --> Ys + Ni3 Ti and )’A -> )’c + (Fe, Ni)2Ti, complete simultaneously with one
another.
Continuous Precipitation
The discussion of this mode of transformation, characterized by long range
diffusion of solute atoms through the metastable matrix phase to the particles of
Annual Reviews
342 MEYRICK ~ POWELL
INCOHERENT RIMOFFINE
(z- X BOUNDARY
PE~
~’-X GRAIN
BOUNDARY
(a) (b) (c) (d)
Figure13 Formationof pearlite froma ferrite, allotriomorph.

Figure 14 Mechanismsby which the in- Figure 15 Nonequilibrium solvus lines

terlamellar spacing of pearlite maybe for the cellular reaction in Fe-Znalloys
changed(after Hillert, 37). (after Speich,25).
the new phase, considers the following topics: morphology of the precipitate,
mechanismand kinetics of growth, and sequential precipitation.
At relatively low degrees of undercooling, nucleation of the new phase tends
to occur predominantly at grain boundaries and at dislocations within the
volume of each grain; at high degrees of supersaturation, on the other hand,
precipitation tends to occur more generally throughout the structure because of
the lower free energy barrier to nucleation. The structure of grain boundary can
Annual Reviews
have a significant effect on the morphological development of the precipitate

particles. For example, Toney & Aaronson (45) found that in (110) misoriented
bicrystals of an Fe- 1.5 wt.% Si alloy allotriomorphs of austenite form whenthe
misorientation 19 is greater than 11°, but when O <~ 11° idiomorphs are the
predominant morphologywith occasional stubby primary sideplates and allotrio-
mophsbeing observed. In the case of grain boundary precipitation in an Ag-
5.6 wt.% A1 alloy (46), primary sideplates form at boundaries between grains
misoriented by less than 17°, allotriomorphs again being the predominant
morphology at high angle boundaries (Figure 16). The ability of high angle
boundaries to support the growth of allotriomorphs must be associated with the
enhanced diffusivity at such boundaries. Whylow angle boundaries should

provide suitable sites for the growth of sideplates is not clear, but one factor may
be the ability of these boundaries to act as sources of dislocations which maybe
required to form a semieoherent matrix-product interface.
LU X500
X250 (10rain.)
X250(4 rnln.) (16 mi~)
Prirn~lry
$ideplates
I0 20 30 40 50 60
R = X~’~ y2÷ Z=
Figure 16 Variation of precipitate morphologywith grain misorientation R. X, Y, and Z

are the minimumrotations (degrees) required to bring the lattices of the abutting grains
into coincidence(after Hawbolt&Brown,46).
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344 MEYRICK a POWELL
Dislocations also are favored nucleation sites at low degrees of undercooling.

Thus at high aging temperatures Phillips (47) observed the growth of triangular-
shaped platelets of Ni3 A1 along dislocations in the matrix of an Ni- 12.7 at.% A1
alloy. The hypotenuse of the particles was coincident with the dislocation line;
because of the size of aluminumatoms it was anticipated that they should cluster
along the tensile side of the dislocation lines. In the case of the precipitation of
metastable y’-Ni3 Ti particles in a nickel-based alloy, the hexagonal y’ particles
nucleate at dissociated dislocations in the fcc matrix, the interaction betweenthe
particle and the dislocation being primarily chemical rather than elastic in nature
(48). Heterogeneous nucleation has been reviewed recently by Nicholson (49).
Mathematical analyses of the growth of allotriomorphs are based normally on

an idealized particle shape (juxtaposed elliptical caps, oblate ellipsoid, etc) and
an assumeddiffusion path (either volumeor interface diffusion or a combination
of both). For those models based on long range volume diffusion directly to the
growing allotriomorph, the resulting kinetic equation(s) and the experimental
growth data can be combined to yield a value of the apparent diffusion
coefficient Dapp . If Dapp = Dv then this result essentially establishes the validity
of the model. Onthe other hand, if Dapp >> Dv the growth rate is too high to be
accounted for by volume diffusion directly to the allotriomorph and consequent-
ly the assumption regarding the diffusion path must be modified. Thus Aaron &
Aaronson (50) found that at low homologous temperatures (0.54-0.69 of
absolute solvus temperature) the allotriomorphs in an Al-4 wt%Cu alloy grow
at rates muchtoo high (Dapp/Dv ~ 500) to be accounted for by volume diffusion
directly to the 0 particles; they proposed that growth occurs rather by a right-
angle collector plate mechanism (Figure 17). Copper atoms move by volume
diffusion to an a-a grain boundary where the atoms diffuse along the boundary
to the edge of the O allotriomorph; thickening of the allotriomorph requires
additional diffusion of the copper atoms along the c~-O interface. The thickening
and lengthening of the particles were found experimentally to vary as t 1/3 and
t I/4 respectively. The collector plate model predicts a t I/4 dependence for
lengthening but a t 1/2 dependence for thickening; the slower than predicted rate
of thickening was associated with the tendency of the O allotriomorphs to
develop facets. As the aging temperature increases the contribution of volume
diffusion directly to the 0 particle increases and, at homologoustemperatures
greater than 0.91 of the absolute solvus temperature, growth is controlled solely
by volumediffusion directly to the precipitate as Dapp = Dv (51). AS pointed out
by Goldmanet al (51) no analysis of allotriomorphic growth that combines both
direct volume diffusion and the contribution of the collector plate mechanism
has been made.
The kinetics of thickening of ferrite allotriomorphs in a high purity Fe-
0.11 wt% C alloy has been investigated by Kinsman & Aaronson (52) using
thermionic emission microscopy. The thickness varies parabolically with time
(s = K tl/2). Goodagreement was found between the experimental rate constant
K and the theoretical value predicted by a growth model based upon volume
diffusion of carbon through the surrounding austenite. During the early stages of
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D
V
Y
l)
V
I ~
e o
Figure 17 Collector plate mechanism
ron &Aaronson,50).
for
the growthof an allotriomorph(after Aa-
~ ADVANCING8 GROUP
X
I----’~" RETREATING
e GROUPS
~
~ /8 CRYSTAL i CRYSTAL
REACTION
~RT_~EIOT
K~
~
REACTION
(o) (b)
Figure 18 Thea + O’ to a + 0 transformationin a Cu-Alalloy (after Laird &Aaronson,

54).
growth the lengthening of ferrite allotriomorphs takes place at a constant rate

and, here again, the kinetics of lengthening appears to be consistent with growth
control by volume diffusion of carbon through the austenite. The addition of a
substitutional alloying dement to an Fe-C alloy might slow downthe thickening
kinetics of ferrite allotriomorphs due to a solute drag effect on the ferrite-
austenite interface. Kinsman& Aaronsonhave suggested that this effect produc-
es the bay in the time-temperature-transformations (TTT) diagram of an Fe-
0.11% C-1.95% Mo alloy. The moving interface of a ferrite allotriomorph is
assumed to be of the disordered type and therefore the growth rate is dependent
upon such factors as interface and bulk compositions, diffusivities, etc. The
broad faces of Widmanstatten ferrite may be dislocation interphase bouridaries
whosemobility normal to the plane of the boundaryis highly restricted. If this
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346 MEYRICK ~ POWELL
is actually the case, then the rate of thickening of Widmanstattenferrite should

be less than that associated with carbon-diffusion-controlled motibn of a
disordered ferrite-austenite interface. Measurementsof the thickening of ferrite
platelets using thermionic emission microscopy confirm this conclusion. In
addition the platelets were observed to thicken by the motion of superledges
along the broad faces of the platelets in agreement with Aaronson’s theory for
the development of the platelet morphology. However, the formation of Wid-
manstatten ferrite has been shown to produce surface tilts (53), an effect
associated with a martensitic transformation. This fact alone makes our under-
standing of the growth of Widmanstatten ferrite uncertain and calls for further
research on this transformation.

The reaction path by which a metastable phase attains the equilibrium state
may involve formation of transition precipitates which are eventually replaced
by the equilibrium second phase. In an AI-4 wt.% Cu alloy the precipitation

sequence is Guinier-Preston (GP) zones --> 0" --> 0’ --> O (CuAI2); both 0’ and
are body centered tetragonal (bct). The mechanisms by which 8’ is replaced by
/9 in the temperature rangeof 325--430°C have been investigated by Laird &
Aaronson (54) using hot-stage transmission election microscopy. A nucleus of/9
forms in a small proportion of the /9’ plates and subsequent growth yields a
platelet of/9 with its broad faces either parallel to or at an angle to the broad
faces of the 8’ plate (Figure 18). In this situation the /9 grows by the direct
transformation of /9’ to /9 (reaction 1 of Figure 18) and by growth into the
metastable a matrix (reaction 2); the latter reaction may be accompanied
simultaneous dissolution of noncontiguous as well as contiguous /9’ plates
(reaction 3). The majority of the O’ plates, however, do not contain a 8 nucleus
and these particles simply undergo dissolution by countercurrent diffusion to
neighboring but noncontiguous/9 particles. Dissolution of the/9’ plates occurs by
a ledge mechanism(55). The structure of the ledges is unusual in that the ledge
contains an edge dislocation whose Burgers vector, a (100), is normal to the
broad face of the plate; this structure differs from that of the growth ledge~ of/9’
plates. The decomposition of an Al-15 wt.% Ag alloy is another example of
sequential precipition. Spherical silver-rich GPzones which form initially begin
to dissolve when heterogeneous nucleation of the transitional 3" phase occurs
(56). The 3" phase in turn undergoes dissolution when particles of the stable
phase form. Both the growth and dissolution of 3" and the growth of )t involve
ledge motion along the broad faces of the particles.
MARTENSITIC TRANSFORMATIONS
Introduction
Despite the effort devoted to the study of martensitic transformations, their
nature remains to be completely elucidated. No general theory is known into
which all the accumulated data can be satisfactorily integrated and which is
capable of convincingly explaining aspects, such as the nucleation event, that still
defy direct observation. The situation is further clouded by the existence of
multiple terminologies and the lingering confusion as to what constitutes a
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correct and sufficient definition of a martensitic transformation.

The latter question has been the subject of much discussion (1, 57, 58).
desirable definition would be one couched in terms of observable characteristics
that wouldprovide a criterion for the unequivocal identification of a martensitic
transformation. The crux of the problem is in the requirement that the
characteristics be unambiguousand, for complete satisfaction, capable of being
formulated into a concise definition sufficient in itself and needless of extensive
clarification.
Transformations that are accepted as martensitic can occur during quenching,
as in manysteels, but so also can the massive transformation. In somematerials
the transformation takes place under isothermal conditions, the fraction trans-
formed increasing with time as happens in interface-controlled diffusional
transformations in some polymorphic changes (59). That the product of
martensitic transformation is related to its parent through a habit plane and

definite orientation relationships is again inconclusive, as the same can often be
true for precipitation from solid solution.
It has frequently been stated that the most definitive manifestation of a
martensitic transformation is the topographical relief it produces on an initially
fiat surface. For this to be true it is necessary that the relief be of a character
peculiar to a martensitic transformation and distinguishable from that arising
from transformations that are clearly not martensitic. Surface relief caused by
martensitic transformations can be described phenomenologically as arising
from a macroscopically invariant plane strain. This observation is the basis of
crystallographic theories of the transformation and has been implicit in defini-
tions of martensite (58). Its importance has been reemphasized in a recent
discussion (53) of surface relief effects in which a definition drawing more
specifically upon crystallographic theories was offered. As an illustration the
salient points of existing descriptions can be incorporated into a general though
cumbersomestatement: a martensitic transformation is a structural change
generated by atomic displacements and not achieved by diffusion, corresponding
to a homogeneousdeformation which may be different in small adjacent regions,
and which gives rise to an invariant plane strain through which the parent and
product are related by a substitutional lattice correspondence, an irrational habit
plane, and a precise orientation relationship.
A martensitic transformation can produce a structural change without change
in composition, which implies there is no necessity for long range diffusion.
Furthermore, all first order phase changes that are agreed to occur without the
need for diffusion are called martensitic. It can be argued then that a martensitic
transformation can be formally defined as a first order phase transition in which
the newstructure grows without the necessity of atom interchange by diffusion.
The complexity surrounding an operational definition for the martensitic reac-
tion can be regarded as a consequence of the search for characteristics that
establish the lack of control by diffusion. Attempts to tie the definition more
stringently to the phenomenological theories seem unwarranted until such
theories becomecompletely successful. Because there is no a priori reason for a
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system to follow only a single path of transformation somehybridization is to be

expected, particularly under conditions where diffusion can occur reasonably
rapidly. Thus the creation of additional terms such as quasimartensite (5) does
not serve to clarify the issue.
The discussion of the martensitic transformation considers the following
topics: morphology of the product, original formulations of the phenomenolog-
ical theory, comparison of the theory with experimental data, modifications of
the theory, microstructure of martensitic crystals, and mechanismof the trans-
formation.
The Morphology of the Martensitic Product

The crystals of the new phase display a variety of morphological characteristics
dependent upon the chemical nature of the parent and the crystallographic
structural change accomplished, which are consequences of the operative mech-

anism of transformation and the influence of the elastic and mechanical
properties of the matrix.
Monocrystalline samples of some alloys of Au-Cd(60) and In-T1 (61) can
caused to transform so that the parent and product are separated by a single
interface (the habit plane) which, upon migration, creates a single crystal of the
martensitic phase, composedof a stack of twins visible by optical microscopy.
More usually a number of martensitic crystals are formed within the parent and
are influenced by the constraints of the matrix. In this respect there are
transformations which take place at the free surface of the specimen (62-64)
which can be expected to differ in character from those representative of the
bulk.
In some simple cases the transformation yields parallel sided bands of new
phase as in the fcc ~ hcp change in cobalt and cobalt-nickel alloys (65). More
usually the martensitic crystal takes the form of a lenticular plate (Figure 19).
Often such plates exhibit a structural discontinuity, called a midrib, on the
equitorial plane. This morphology is one of the variants adopted by the
martensitic products in iron-based alloys. The term plate martensite is adopted
for this variant in keeping with a recent description of the morphologyof ferrous
martensites (66). Martensitic plates generally form at angles to neighbors and
so doing subdivide the matrix so that plates formed subsequently are reduced in
size. Accordingly, growth is frequently inhibited by mutual impingement which
can cause mechanical twinning (66) and microcracking (66, 67) as well as plastic
deformation.
Many workers have demonstrated the occurrence of plate martensite in a
number of concentrated binary alloys of iron and steels (68-72). On the other
hand, the product of the martensitic transformation in a variety of dilute iron
alloys (73, 74) cannot be described as plate-like. Instead the microstructure
composedof blocky units several microns in size (Figure 20) made up of fine
parallel martensitic laths. Neighboring groups of laths can be twin-related or
separated by high or low angle boundaries. During formation the laths partition
the matrix as does plate martensite but, unlike the latter, subsequent laths tend
Annual Reviews

Figure I9 Plate martensite in an Fe- 13.9%Mn alloy. X 1OOO.
P,
Figure 20 Lath martensite in an Fe-0.31%W alloy. X200.
to form in parallel orientations. This variant of the morphology has also been
christened many names; the term lath martensite will be used herein.
The essential features of the morphologies described above have been well
established. With the exception of detailed shape change measurements yet to be
discussed there seems little more information that might be gathered by optical
Annual Reviews
microscopy. Indeed the individual components of lath martensite and the

substructure in plate martensites are generally too fine to be thus studied
profitably.
The fact that the transforming region undergoes bbth a change in crystallo-
graphic structure and in shape, with consequent modifications of the surface
topology, while maintaining contiguity with the surrounding matrix, gives rise to
several other important morphological aspects. The first of these is the shape
change itself. Its chz, racter is deduced from measurements made upon the
exterior surface of the specimen and thus is subject to the doubts that can arise
concerning the relationship of such observations to bulk phenomena.Apart from
cases where the depth of penetration of the martensitic crystal is small, as in the
surface martensites mentionedearlier, it is not clear that such doubts are valid.
The fact that there can be very good agreement between the predictions of
twinning theory and surface topography (75) lends strong support to the
argumentthat indications from the surface can be descriptive of the bulk; so also
does the fact that the phenomenologieal crystallographic theory successfully
describes some fully twinned martensitic products. The nature of the shape
change is deduced by use of interference microscopy and by measurements of its
effects upon prescribed lines upon the parent surface. Early results (76) which
demonstrated that the topographic changes accompanying a martensitic transi-
tion are consistent with those that would be produced phenomenologically by a
macroscopically invariant plane strain, in which the invariant plane is the habit
plane, have been substantiated subsequently in a number of systems. The habit
plane is usually an irrational plane of the parent and is characteristic of the
material concerned, as are the orientation relationships. These macroscopic
characteristics form the basis of the crystallographic theories.
Original Formulations of the Crystallographic Theory
The basic crystallographic theory originated in the early 1950s (8, 9) and has
been frequently described in detail since (1, 72, 77). It pays no direct attention
to atomic mechanisms but has as its aim the construction of a transformation
strain which, when applied to the parent crystal, produces phenomenologically
the results of the martensitic transition. The original theories are mathematically
equivalent but differ in formulation.
The shape strain T can be written in matrix notation as T = RBP. Of these B
is the Bain strain which transforms a selected unit cell of the parent into one of
the product. For example, in carbon steels the strain
~/ 0
0 03//
applied relative to orthonormal axes parallel to the [1]0], [110], and [001]
directions in the fcc structure yields the bet structure. The bet unit cell of the
Annual Reviews
latter has its [100], [010], and [001] edges parallel to the system of axes and of
magnitudes a~/.v/2, a~/~/2, and a~3, being derived from the bet cell of the fee
structure outlined by the edges 1/2 a[l~0], 1/2 a[ll0], and a[001]. In this
example all atoms are movedto their new positions by B; however, for structures
which have primitive cells containing different numbersof atoms, only a fraction
are correctly movedand the remainder require additional shuffles (78, 79). The
choice of B has to be made from an infinity of possibilities without clear
guidance other than the intuitively plausible criterion of minimal principal
strains. Its application does not in general accomplish the lattice change and at
the same time leave a plane both unextended and unrotated. To conform to the
macroscopic requirement of a homogeneousinvariant plane strain, additional

strains are required. These must leave the lattice unchanged and comprise a
rotation R and a shear P chosen so that T has an invariant plane. P can refer to
a strain accomplished by slip or twinning (which have equivalent mathematical

descriptions) and, as written above, is applied to the matrix phase.
The evaluation of the strain T can be performed either graphically upon a
stereographic projection or through formal matrix algebra. Details of both
procedures are presented in the referenced work. In essence the solution requires,
first, the choice of a suitable correspondencebetween two cells of the structures
and the numerical expression of B from lattice parameter measurements. Second,
a shear plane and direction are assumed and the magnitude of shear is found so
that BP yields a macroscopically unextended plane. Finally the matrix R which
ensures that the unextended plane remains unrotated is obtained.
Comparison of the Theory With Experimental Data
The most obvious output from the crystallographic theory is the identification of
the habit plane (i.e. the invariant plane) and the orientation relationships
described by R. Significant failure to predict correctly these parameters consti-
tutes grounds for rejection of the theory as formulated. On the other hand,
success does not immediately indicate a completely satisfactory description as
this also requires internal consistency with the magnitude and direction of the
shape strain and the martensitic substructure (80). In this respect the invariant
plane strain T can.be written as T = I + mtlp’ whereI is the unit (3 × 3) matrix,
m is the scalar magnitude of the strain, and d and p’ are unit vectors defining
respectively the displacement direction and the invariant plane normal.
Although the theory takes no formal cognizance of atomic mechanisms, the
manner by which P is achieved can be expected to influence the mierostructure
of the product. This can be appreciated physically by realizing that the strain RB
applied to a small region creates a product of the correct structure and
orientation. With increase in its size the buildup of macroscopicdistortion in its
interface is avoided by the operation of P. If the choice is twinning in the
martensite, the latter can be expected to consist of a stack of twins. In this case
two martensitic orientations exist equivalent to the operation of two crystallo-
graphic variants of the Bain strain in volumes separated by a twinning plane
Annual Reviews
generated from a plane of symmetryin the parent (81). If P is by slip, one variant
of B is to be expected, and twins ought to be absent, but the microstructure may
contain planar faults.
The precise determination of all the parameters relevant to testing the theory
is by no means a trivial operation and, in manycases, is beset with severe
difficulties. Nevertheless the accumulated data, though sometimes incomplete,
demonstrate the fit of theory to fact to range from excellent, through fair, to
inadequate. Detailed reviews of the situation for transformations in pure
elements and in alloys have been published (l, 72).
In general the theory affords an excellent description of cases where the
macroscopic and microscopic characteristics are well defined and relatively

simple; but as these characteristics, particularly from the microstructural aspect,
become irregular and increasingly complex the theory becomes progressively
inadequate. Excellent agreement is found for the allotropic transformation in

cobalt (72) and for the more complexstructural changes in Au-Cd,In-T1 (77),
-33%Ni, Fe- 22% Ni-0.8% C, and Fe-24.5% Pt (80). The first is simple in that
the lattice change can be produced by a shear in a (1 l~) on every second (11
plane of the fcc phase. The second two have small principal strains and a
substructure of evenly spaced twins visible at least away from the interface by
optical microscopy. On the other hand, the last three have large principal strains
and consist of regularly spaced twins of the correct type visible only by electron
microscopy. The latter three alloys are interesting as they are examples of the
comparatively few ferrous alloys that show convincing agreement with the
theoretical predictions in an internally consistent manner. All three have habit
planes close to (3 l0 15)v which is predicted by the Bain correspondence
mentioned earlier and shear on a (1 l~)(11 l) system in the martensite. Experi-
mentally this is an atypical habit plane when comparedto the near (11 l)v habit
in lath martensite of low-carbon steels and dilute binary alloys, the (259)v habit
of plate martensite in high-carbon steels, and the {225)v habit commonfor plate
martensite in iron containing 0.8-1.4% C.
The variation of habit plane with composition change is further illustrated by
the progessive shift away from (3 10 15)v with decrease in Ni content of Fe-Ni
alloys (82). Whereasthe existence of habits near (259)r and (225)r is presumably
associated with the complex substructure of incompletely and irregularly
twinned plates, the significance of the association is at present unclear.
Modifications of the Phenomenological Theory
Cases of successful application of the theory have been held as a demonstration

of its essential soundness. Consequently, closer agreement with those ferrous
martensites which exhibit habits other than (3 10 15}v has been sought by
modifications of the basic formulation. A commonprocedure (83) which leaves
the basic theory unchangedis to examine the results of alternative choices for
the plane and direction of the lattice invariant shear, but no combination has
proved completely satisfactory.
Annual Reviews
In one of the original formulations (9) somemodification was possible through

the use of an adjustable dilatational parameter ~ incorporated as a factor in the
principal distortions of the Bain strain, which was varied from unity to improve
agreement. This procedure amounts to relaxing the invariant plane condition
and permitting a slight isotropic dilatation in the interface. Althoughan arbitrary
variable is aesthetically displeasing, the possibility of a dilation cannot be
summarily dismissed and its use has been frequent. Recent measurements (84)
have shownthat the required dilatation for the (225}v habit plane in steels does
not exist and in this case at least the dilatation parameter must be discarded.
In recent years there have been four main attempts to modify the theory. All
four have in commonthat the modification involves the introduction of

additional lattice strains and is directed towards an attempt to resolve the
dilemma posed by the {225}v habit. The first (85) considers a composite
martensite plate of twinned and untwinned regions and invokes, besides the
usual R and B, an additional rotation and two shears, but has been shown (86)
to be unsatisfactory. Of the others, one assumes an accomodation shear within
the austenite ahead of the interface (86), while the other two replace the lattice
invariant shear P by two independent lattice invariant shears (87, 88). All three
have been discussed in detail recently (89) with the conclusion that the
modifications improve the overall agreement but not to the state of satisfaction
extant for the {3 10 15}~.
Although the departure from a single simple lattice invariant strain appears
consistent with the increased complexity of the martensitic substructure as the
habit movesfrom {3 10 15}v,one is left with the uncomfortable thought that any
shape change is describable given enough unrestricted combinations of shear;
however, this loses the elegance of the original theory, increases the numberof
initial assumptions, and may well produce a result of dubious value.
The Microstructure of Martensitic Crystals

Electron microscopydemonstrates that crystals formed martensitically are highly
defective and can contain twins, stacking faults, dislocations, and combinations
thereof. Some examples of relatively clear-cut cases in which the product is
completely twinned and is thus composed of a stack of lamellar twins have
already been described. Transformations between close packed structures often
result in heavily faulted products. The product of the fcc to hcp allotropic change
in cobalt is rich in stacking faults, as is consistent with the fact that the structural
change can be obtained by shears of a/6 (11~) on every second parallel {111}
plane. Indeed in situ electron microscopy (90) has shown that perfect disloca-
tions can dissociate producing extended stacking faults during the phase change.
By the same technique it has been demonstrated that arrays of extended
dislocations can be emitted from grain boundaries during the transformation
(91). Similarly the a phase formed from the fcc/3 in lanthanum (92) is densely
faulted. In this case the a is a modified hcp structure with a stacking sequence
ABACABAC,which can be produced from the /3 by displacing two adjacent
close packed planes by a/6 (112) every fourth plane. Heavily faulted structures
Annual Reviews
354 MEYRICK~ POWELL
are also producedin alloys such as those of the extensively studied Cu-AIsystem
(93, 94). Accordingto compositionthe fl phasecan transformto ff or ill. These
can be regarded as arrays of stacking faults although the details are rather
complex; lamellae of the stacking sequences ABCBCACAB, AB, and ABChave
beenidentified (95).
Ferrousalloys exhibit a widerange of microstructuralcharacteristics described
in detail in tworecent reviews(96, 97). Thevariations are intriguing becausethe
basic structural changerequired is generally similar. Broadlyspeaking, plate
martensites can be comprisedentirely of fine twins (80, 98) or consist of twinned
and untwinnedregions (99-101), the latter containing dislocations, while lath
martensite is usually composedof bundles of elongated subgrains characterized

by complexdislocation structures (102-104), although twins have also been
detected (105). In all completely twinned martensitic crystals that are well
described by the crystallographic theory, the types of twins observed are

consistent with the lattice invariant shear invokedin the theory, fromwhichit is
inferred that such twins are direct consequencesof the modeof transformation.
This is also a reasonableinference for the presenceof stacking faults in other
martensites. For steels the proper twin is of the {112}btype whichis observedin
all twinned products. However(011)b twins are also found in incompletely
twinned bct martensite (100, 107) and the {l12)t ~ twins can themselves be
internally twinned(96, 108). In addition twins sometimesappear (106) to
been modified by slip processes. This has been used to explain the apparent
deviation of twins fromthe ideal .(112}b in Fe-Ni(109), but such deviations
also arise fromexperimentalerror (110). It can be seen that the complexitiesare
such that a complete documentation of the microstructural features awaits
further painstakingstudies.
Evenwith a complete description of the microstructural features a luther
major problemarises concerning their origin. One issue here is: which are
necessary ingredients of the cransformationper se and whichare consequences
of the matrixconstraints?"[ he latter are said to correspondto a post-transforma-
tion strain, althoughthey can presumablyarise to someextent concurrently. In
this respect it has beenargued(106) that {01l}b twins are indirect products
the transformationas they wouldbe derived froma nonmirrorplane via the Bain
correspondence.Twinnedtwins are observedin foils prepared from the bulk and
also in those transformedin situ whenthe influences of the bulk are minimized
(although other kinds are substituted) and have thus been claimed (108) to
consequences of the modeof transformation. The role of dislocations is
problematicalbecause any directly involved in promotingthe structural change
oughtto be retained at the interface.
The Mechanismof the Transformation
Amajor area of martensitic transformationsin whichsatisfactory understanding
is lacking concerns the physical mechanismsby which the newphase nucleates
and grows. In all heterogeneoustransformations the growthof the newphase is
profoundlyinfluenced by the nature of the interface that separates it from the
Annual Reviews
matrix. (In this context heterogeneous transformation implies that at any instant
the system can be divided into transformed and untransformed volumes.) This is
especially true of a martensitic transition in which the interface moveswithout
the aid of diffusion and, as a result of its movement,creates the new phase. Its
origin nature and behavior are thus central to understanding the mechanismsof
the transition. It is generally supposedthat the interface is glissile and is formed
by a suitable array of dislocations or by the termination of a stack of twin
lamellae. Indeed discussions of the various characteristics exhibited by ferrous
alloys are based upon the effects of the pertinent vari.ables upon the competitive
processes of slip and twinning. As a general trend it can be stated that the
departure from well-defined, completely twinned plates, to lath martensite is

associated with an increase in the Ms temperature and a reduction in alloying
content, which are of course interconnected, particularly with respect to austen-
ite stabilizing elements. To the extent that these changes would be expected to
favor slip processes over twinning, the correlation is qualitatively reasonable.
Oneof the early versions of the phenomenological theory (111) in~,olved the
formal concept of surface dislocations, whereas the first specific model attempt-
ing to describe the austenite-martensite interface in terms of an array of screw
dislocations appeared earlier (112). Other models have been proposed subse-
quently, including dislocation pole models (113) for the fcc to hop transition.
More recently models of dislocation arrays and their interaction with solute
atoms have been considered (114). Although much progress has been made
recent years in resolving the physical details of a variety of boundaries and
interfaces (115) there exists very little factual knowledge, gained by direct
observation, of the structure of martensitic interfaces, a lack that is particularly
acute for ferrous lath martensites.
The complexities of the problem are further compoundedfor transformations
constrained within the matrix bulk as, for example, in ferrous plate martensites.
Although the interface separates the new phase from the matrix, growth has
occurred such that the equatorial dimensions of the lenticular platelet greatly
exceed its thickness. This raises the question of the processes leading to the
generation of the interface and introduces the topic of nucleation phenomena.
The status of nucleation ideas has been recently reviewed in detail (3). Classical
nucleation theory applied directly is inadequate and the existence of large
embryos capable of being rendered supercritical by quenching has not been
demonstrated. It appears that the formation of nuclei is heterogeneous and can
be autocatalitic, but, although imperfections such as stacking faults have been
associated with the initiation process, the nature of the heterogeneoussites is not
fully understood. In this context it is worth noting that these ideas consider
tacitly a static lattice. It is well known(116) that as the temperature is changed,
softening of special elastic coefficients of a crystal can occur associated with the
approaching mechanical instability of the crystal structure, which results in high
amplitudes of certain modesof lattice vibrations. These effects can be detected
by diffraction techniques before the onset of the macroscopically observable
transition [as, for example,in TiNi alloys (117)]. In the latter reference the effects
Annual Reviews
were termed "premartensitic" although it seems reasonable to suppose that they,

perhaps in conjunction with crystal defects, might lead directly to the onset of
the transformation.
HYBRID TRANSFORMATIONS
The transformations that have been described so far are mainly examples of
"pure" transitions in that they can be separated convincingly according to
mechanisms and resulting morphologies. There exist transformations which
cannot be completely satisfactorily placed in one or other of these categories but
instead incorporate characteristics pertaining to two or more of them. In these

cases the transformation is accomplished by a mixture of modes and the total
effect is logically regarded as a hybrid transformation. In the following, the
salient features of two such examples will be presented. The first of these is
ferrous bainite, for which the discussion will consider in order its morphology,
kinetics, a~ad mechanismsof growth. As a second example, the processes taking
place during the growth of ~’ and -/precipitates in A1-Agalloys will be outlined.
Bainite
The name bainite was coined for the microstructural product that forms in steels
when austenite is transformed under conditions that largely preclude the
formation of martensite or pearlite. It consists of an aggregate of ferrite and
discrete particles of iron carbide. As such, it is an accepted term and excludes
other ferrite and alloy carbide aggregates that can arise in alloy steels (118).
Because the actual processes that take place during the formation of bainite are
not those that are purely martensitic nor those that yield pearlite, it has become
customary to refer to them as comprising a bainitic transformation. In some
ways. this has been unfortunate, perhaps because such a terminology suggests
that it represents a separable transformation possessing its ownunique charac-
teristics. Indeed, in addition to those aspects of the topic that are themselves as
yet unresolved, controversy exists over the definition of the bainitic transforma-
tion. This has been the subject of two recent publications (119, 10) in which can
be found a rather comprehensive bibliography of relevant literature.
The details of the morphology vary gradually with the temperature at which
the reaction takes place making it difficult to identify any unique outstanding
characteristics. In the upper range of temperature the product appears feather-
like in the optical microscope and is composedof aggregates of parallel groups
of ferrite" laths, amongwhich, on the intercrystalline boundaries, lie cementite
plates oriented parallel to the local boundaries. Apart from the presence of
carbides the microstructure on the scale viewed within the electron microscope
is quite similar to that of ferrous lath martensites. Onthe other hand, at lower
temperatures the ferrite plates adopt a more acicular aspect and carbides
oriented at about 60° to the main axis are found both within the crystals and in
contact with the intercrystalline boundaries. The two extremes are called upper
and lower bainite respectively. Whereas a sharp division between the two
Annual Reviews
variants does not appear to exist universally, it seems in general that the two
regimes lie on either side of approximately 350°C. These observations refer to
the final products. Litde is knownof the precise sequence of events that leads to
the final microstructure, although in lower bainite metastable carbides other than
cementite have been observed.
The ferrite componentof the microstructure produces relief effects on initially
flat surfaces, thus indicating the presence of a macroscopic shape change which
must therefore be explicable in terms of any mechanisn proposed for the mode
of growth.
In plain carbon steels the conditions under which the product of the
transformation is pearlite or bainite merge together gradually; however, in alloy

steels the processes can becomeseparable and whenthe obscuring effects of the
pearlite morphology are avoided there is found to exist a temperature, the B s
temperature, which marks the upper limit of the temperature range in which
bainite can form during isothermal holding. Abovethe Bs bainite will not form;
however, it can form in increasing amounts at temperatures increasingly further
below it. The Bs temperature is somewhatanalogous to the Ms temperature, an
analogy that is strengthened by the fact that bainite can be induced to form
above the Bs temperature by the application of stress, as can martensite above
the Ms temperature. The growth rate of individual ferrite plates is slow and is
anisotropic in that the thickening rates are exceeded by the rates of lengthening.
As is commonlytrue in solid state phase transformations the details of the
atomic movements involved in the production of the new microstructure have
eluded direct observation. All that can be determined with some certainty are
end consequences of the events, from which deductions concerning the modeof
transformation are perforce made. The more complex the consequences, the
greater the difficulties that beset attempts at interpretation.
The two primary consequences of the processes that form bainite are a matrix
structural change from fcc to bcc and the appearance of carbide particles. Two
main schools of thought exist concerning the manner by which these conse-
quences are accomplished. Both accept the fact that the carbide particles indicate
that long range diffusion of carbon is undoubtedly involved, but diverge in
opinion regarding the origin of the ferrite. On the one hand, the similarities in
microstructure exhibited by bainitic ferrite and martensite, the occurrence of
surface relief effects, and the fact that as the temperature is lowered the accepted
martensitic transformation begins, have led to the opinion that the structural
change might be accomplished by a martenstic transformation relating the
substitutional atoms. In this hypothesis the substitutional atoms are converted to
the bcc structure by a diffusion!ess martensitic process. The slow growth rate is
rationalized either by invoking a series of small rapid events interspersed by
periods of quiescence or by a continuous slow advance, with the overall rate
being controlled by carbon diffusional processes,
The opposing view discounts any contribution to the growth of ferrite from
martensitic processes. Instead, lengthening of the individual ferrite units is
deemed to arise from the repeated nucleation of incoherent ledges in the
Annual Reviews
358 MEYRICK¯ POWELL
interface and the lateral migrationof these by substitutional diffusion. Againthe

rate controlling processfor thickeningis thoughtto be diffusion of carbonin the
austenite.
In these views the major clash arises in the mannerof ferrite formation,
whereasthe precipitation of the carbides is, in the main, subject to less serious
differences of opinion, althoughwhetheror not the precipitation takes place in
the ferrite as well as in the austenite is relevant to the former.Becausethe answer
is not directly knowninferences are drawnfrom indirect observations and are
thus open to doubt. That cementite in upper bainite forms from austenite
appears to be generally accepted; however,opinions diverge on the question of
the cementite and epsilon carbides in lower bainite. The morphologyof the
carbides within the ferrite plates and the similarities with temperedmartensite
havebeentaken to infer the initial formationof supersaturatedferrite followed
by carbide precipitation therein. So far experimentalobservationshavefailed to

demonstratethe existence of this supersaturation, but this cannot be unhesita-
tingly taken as proof of its absence.Thealternative viewis that the carbidesare
moreor less alwaysformedinitially at the ferrite-austenite interface. It would
seemthat this is an importantpoint as such carbides mightwell be engulfed by
an interface migrating by a diffusional mechanism,but provide barriers to a
glissile interface.
Probablythe greatest single contribution to the adoption of the martensitic
viewpointis the surfacerelief associatedwiththe bainitic ferrite. In this regard,
also, the situation is confused and little if anything can be unequivocally
concluded. As discussed before, part of the confusion arises from the need to
provethat the surface relief necessitates a martensitic contribution. Theopposite
view requires substantiation by a convincingmeansof producingrelief of the
type observed other than through a martensitic mode. Applications of the
phenomenological crystallographic theory of martensite fail to providea consist-
ent description; however,this is true for all except the well-behavedof the
ferrous martensites and consequentlythe application of a theory that is known
to be largely inadequatefor ferrous materials is hardly to be expectedto provide
a reliable meansof decidingfor or against a martensitic contribution.to bainitic
ferrite.
Becausethe precise modeof growthof b~initic ferrite has not been established
with certainty, further details of the process will not be considered here.
Whateverthe mechanismby whichby which the ferrite is produced, the overall
transformation is composedof at least two separate modes. It involves the
simultaneousproduction of two phases; one, the carbide, is formedby contin-
uous precipitation from one or both of the matrix phases, and the second, the
bcc ferrite, is producedby an allotropic transformation.
The Formationof 3" and "/in AI-Ag Alloys
In the section dealing with continuousprecipitation reactions the AI-Agsystem
was mentioned as an example of a system in which sequential precipitation
reactions are observed, namelyGPzones, metastablehop ),’, and the stable hcp
Annual Reviews
~, phase. In all three the newphase is enriched with silver as comparedwith the
matrix; consequently, substitutional long range diffusion is obviously a necessary
ingredient in the processes. In addition, for the -~’ and ~ phases a structural
transition of fcc to hcp occurs. In this case the details of the process have been
studied by careful investigations using hot-stage transmission electron microsco-
py which has revealed that whereas the overall rate of the processes is diffusion
controlled, the structural change is largely madethrough displacive rather than
constructive mechanisms.
Nuclei of the 3" phase form heterogeneously (56) at dislocations which, at the
onset of the transformation, dissociate into pairs of glissile partial dislocations
.connected by ribbons of stacking faults. With additional ageing the partial

dislocations are able to separate further because, as is a reasonable supposition,
silver atoms migrate to the fault providing a reduction in energy. Growthin the
direction normal to the close packed plane is accomplished by the formation of

more glissile partials every second (111) plane and their subsequent migration
that plane. The reverse sequence occurs during dissolution when the temperature
is raised. The total growth process involves three steps, the nucleation of partial
dislocations, the diffusion of Agto them, and their migration in the habit plane.
The rate of dislocation migration is controlled by the substitutional diffusion;
but in this case the thickening rate of the platelet occurred more slowly than
permitted by diffusion, from which it was concluded that the nucleation of the
dislocations was the rate controlling process.
The characteristics of the formation of the stable 7 phase in A1-Agalloys have
been examined in several recent investigations (120, 121). It forms as approxi-
mately hexagonally shaped plates whosebroad faces, parallel to the {111) planes
of the matrix, contain dislocations. These sometimes become arranged into
stable networks which results in a markedreluctance for the plate to thicken;
otherwise thickening is accomplished by the generation and migration of arrays
of interface dislocations. Dislocations are formed during the lengthening of the
platelet which apparently also involves the operation of a migrating ledge
mechanism. Indeed, superledges of the order of 1130 A in magnitude were
observed to propagate around the circumference of some platelets.
In bulk samplesthe emergenceof 3’ plates at the free surface is associated with
surface relief which, at least initially, is consistent with a plane strain. During
prolonged annealing the surface tilts decrease somewhat in magnitude as
processes take place that tend to relieve the strain energy.
It is evident from the foregoing that both the "t’ and ,/phases are produced by
hybrid transformations in the sense used in this article. At least part of the
structural change is accomplished by a displacive process, namely the glide of
partial dislocations. Such a process, if it took place in the complete absence of
diffusion, wouldclearly be martensitie. This is not so in this case wherethe rates
at which the dislocations glide and at which the concurrent compositional
changes are effected are dependent upon the diffusion of silver and aluminum
atoms. The total transformation is not, however, attained by diffusional recon-
structive processes. In detail, then, the events can be considered hybrid, although
Annual Reviews
360 MEYRICK ,~ POWELL
the overall process is one of continuous precipitation, in the sense that discrete
particles nucleate heterogeneously within the matrix and grow more or less
continuously in a manner controlled by diffusion, influenced by special interface
characteristics.
ACKNOWLEDGMENTS
One of us (G. M.) is grateful for the support of the U. S. Army Research Office
(Durham). In addition, the authors wish to thank the following for permission
use figures from their published works: G. Krauss and A. R. Murder; R. A.
Fournelle and J. B. Clark; T. B. Massalski, J. E. Kittl, and E. B. Hawbott; G. H.

Goodenow and R. F. Hehemann; J. W. Spretnak, E. Eichen, and J. F. Mortal;
and K. N. Tu and D. Turnbull.
Literature Cited
1. Christian, J. W. 1965¯ The Theory of 15. Goodenow, R. H., Hehmann, R. F.
Transformations in Metals and Alloys. 1965. Trans. AIME233:1777
New York: Pergamon 16. Eichen, B., Spretnak, J. W. 1959. Am.
2. The Institute of Metals. The Mecha- Soc. Metals Trans. 51:454
nism of Phase Transformations in Me- 17. Bharucha, V., Mancini, G. A., Powell,
tals, 1969. Monogr. Rep. Ser. No. 33. G. W., Spretnak, J. W. 1961. Trans.
London: The Institute of Metals AIME 221:498
3. Am.Soc. Metals. 1970. Phase Transfor- 18. Hawbolt, E. B., Massalski, T. B. 1970.
mations. Metals Park, Ohio: ASM Met. Trans. 1:2315
4. Wayman,C. M. 1971. Ann. Rev. Mater. 19. Karlyn, D. A., Cahn, J. W., Cohen, M.
Sci. 1:185 1969. Trans. AIME245:197
5. Phillips, A. J. 1930. Trans. AIME 20. Massalski, T. B., Perkins, A. J., Jaklov-
89:194 sky, J. 1972. Met. Trans. 3:687
6. Greninger, A. B. 1939. Trans. AIME 21. Kittl, J. E., Massalski, T. B. 1967. Acta
133:204 Met. 15:161
7. Cohen, M. 1951. Phase Transforma- 22. Aaronson, H. I. 1962. Decomposition of
tions in Solids, p. 588. NewYork: Wi- Austenite by Diffusional Processes, 387.
ley NewYork: Interscienee
8. Wechsler, M. S., Lieberman, D. S., 23. Perkins, A. J., Massalski, T. B. 1971.
Read, T. A. 1953. Trans. AIME Met. Trans. 2:2701
197:1503 24. Saburi, T., Wayman, C. M. 1965.
9. Bowles, J. S., Mackenzie, J. K. 1954. Trans. AIME233:1373
Acta Met. 2:129, 138 25. Speich, G. R. 1968. Trans. AIME
10. Hehemann, R. F., Kinsman, K. R., 242:1359
Aaronson, H. I. 1972¯ Met. Trans. 26. Aaronson, H. I., Clark, J. B. 1968. Acta
3:1077 Met. 16:845
11. Owen, W. S., Gilbert, A. 1962. Acta 27. Smith, C. S. 1953. ASMAm. Soc. Me-
Met. 10:45 tals. Trans. Quart. 45:533
12. Zerwekh, R. P., Wayman,C. M. 1965. 28. Tu, K. N., Turnbull, D. 1967. Acta
Acta Met. 13:99 Met. 15:369
13. Bibby, M. J., Parr, J. G. 1964. J. lron 29. Tu, K. N., Turnbull, D. 1967. Acta
Steel lnst. London202:100 Met. 15:1317
14. Speich, G. R., Swarm, P. R. 1965. J. 30. Tu, K. N., Tumbull, D. 1969. Acta
Iron Steel Inst. London203:480 Met. 17:1263
Annual Reviews
31. Liu, Y. C., Aaronson, H. I. 1968. Acta 62. Honma, T. 1951. J. Jap. Inst. Metals
Met. 16:1343 21:122
32. Fournelle, R. A., Clark, J. B. 1972. 63. Klostermann, J. A., Burger, W. E.
Met. Trans. 3:2757 1964. Acta Met. 12:355
33. Hull, F. C., Mehl, R. F. 1942. ASM 64. Klostermann, J. A. See Ref. 2
Am. Soc. Metals Trans. Quart. 30:381 65. De Lamotte, E., Altstetter, C. 1969.
34. Modin, S. 1951. Jernkontorets Ann. The Mechanism of Phase Transforma-
135:169 tions in Crystalline Solids, Monogr.Rep.
35. Modin, S. 1958. Jernkontarests Ann. Set. No. 33. London: The Institute of
142:37 Metals
36. Hultgren, A., Ohlin, H. 1960. Jernkon- 66. Krauss, G., Marder, A. R. 1971. Met.
torets Ann. 144:356 Tram. 2:2343
37. Hillert, M. 1962. Decompositionof Aus- 67. Davies, R. G., Magee,C. L. 1972. Met.
tenite by Diffusional Processes, p. 197. Trans. 3:307

NewYork: Interscienc¢ 68. Brook, R., Entwhistle, A. R. 1965. J.
38. Zener, C. 1946. Trans. AIME167:550 Iron Steel Inst. London203:905
39. Cahn, J. W. 1959. Acta Met. 7:18 69. Bell, T., Owen,W.S. 1967. J. Iron Steel
40. Shapiro, J. M., Kirkaldy, J. S. 1968. Inst. London 206:428
Acta Met. 16:1239 70. Patterson, R. L., Wayman,C. M. 1965.

41. Speich, G. R. 1963. Trans. A1ME Acta Met. 14:347
227:754 71. Tadaki, T., Shimuzu, K. 1970. Trans.
42. Sundquist, B. E. 1968. dicta Met. Jap. Inst. Metals 11:1
16:1413 72. Wayman,C. M. 1964. Introduction to
43. Bolze, G., Puls, M. P., Kirkaldy, J. S. the Crystallography of Martensitic
1972. Acta Met. 20:73 Transformations. New York: Macmil-
44. Fillnow, R. H., Mack, D. J. 1950. lan Series in Materials Science
Trans. AIME 188:1066 73. Chilton, J. M., Barton, C. J., Speich, G.
45. Toney, S., Aaronson, H. I. 1961. Trans. R. 1970. J. Iron Steel Inst. London
.4 IME221: 909 208:184
46. Hawbolt, E. B., Brown, L. C. 1967. 74. Marder, J. M., Marder, A. R. 1969.
Trans. AIME 239:1916 ASM Am. Soc. Metals Tram. Quart.
47. Phillips, V. A. 1966. Acta Met. 14:1533 62:1
48. Oblak, J. M., Owczarski, W. A., Kear, 75. Dunne, D. P., Wayman, C. M. 1970.
B. H. 1971. Acta Met. 19:355 Acta Met. 18:981
49. Nicholson, R. B. 1970. Phase Transfor- 76. Bowles, J. S., Mackenzie, J. K. 1954.
mations, 269. Metals Park, Ohio: ASM Acta Met. 2:129
50. Aaron, H. B., Aaronson, H. I. 1968. 77. Lieberman, D. S. See Ref. 3, p. 1
Acta Met. 16:789 78. Christain, J. W. 1965. Iron Steel Inst.
51. Goldman, J., Aaronson, H. I., Aaron, London, Spec. Rep. 93, 1
H. B. 1970. Met. Trans. 1:1805 79. Christian, J. W. See Ref. 2, 129
52. As discussed and referenced by Aaron- 80. Dunne, D. P., Wayman, C. M. 1971.
son, H. I., Laird, C., Kinsman, K. R. Met. Tram. 2:2326
1970. Phase Transformations, 367, 375. 81. Bowles, J. S., Wayman,C. M. 1972.
Metals Park, Ohio: ASM Met. Trans. 3:1113
53. Clark, H. M., Wayman, C. M. 1970. 82. Ledbetter, H. M., Reed, R. P. 1969-70.
Phase Transformations, 96--101. Metals Mater. Sci. Eng. 5:341
Park, Ohio: ASM
54. Laird, C., Aaronson, H. I. 1966. Acta 83. Crocker, A. G., Bilby, B. A. 1961. Acta
Met. 14:171 Met. 9:678, 992
55. Laird, C., Aaronson,H. I. 1968. J. Inst. 84. Krauklis, P., Bowles, J. S. 1969. Acta
Metals. 96:222 Met. 17:997
56. Hren, J. A., Thomas, G. 1963. Trans. 85. Lieberman, D. S. 1966. Acta Met.
AIME 227:308 14:1723
57. Lieberman, D. S. See Ref. 2, 167 86. Bowles, J. S., Dunne, D. P. 1969. Acta
58. Bilby, B. A., Christian, J. W. 1956. See Met. 17:677
Ref. 2, 121 87. Acton, A. F., Bevis, M. 1969-70. Ma-
59. Becker, J. H. 1958. J. Appl. Phys. ter. Sci. Eng. 5:19
29:110 88. Ross, N. H. D., Crocker, A. G. 1970.
60. Lieberman, D. S., Wechsler, M. S., Acta Met. 18:405
Read, T. A. 1955. J..4ppl. Phys. 26:473 89. Bowles, J. S., Wayman,C. M. 1972.
61. Burkhart, M. W., Read, T. A. 1953. Met. Trans. 3:1113
Trans. AIME 197:1516 90. Votava, E. 1961. J. Inst. Metals 90:129
Annual Reviews
362 MEYRICK ¯ POWELL
91. Kennedy, E., Hirth, J. P. Unpublished 107. Oka, M., Wayman,C. M. 1969. Trans.
work Jap. Inst. Metals 10:411
92. Marinkowski, M. J., Hopkins, F. N. 108. Thomas, G., Das, S. K. 1971. J. Iron
1968. Trans. AIME242:579 Steel Inst. London 209:801
93. .4cta
Swarm, P. ll:Sll
R., Warlimont, H. 1963. 109. Nishiyama, Z., Shimuzu, K. 1961. Acta
Met.
Met. 9:980
94. Wilkens, M., Warlimont, H. 1963. Acta l l0. Patri¢ian, T. J., Ledbetter, H. M.,
Met. I 1 : 1099 Reed, R. P. 1972. Met. Trans. 3:947
95. Delaey, L., Lefever, J. 1969. Trans. lll. Bullough, R. K., Bilby, B. A. 1956.
Jap. Inst. Metals 10:372 Proc. Phys. Soc. B 69:1276
96. Thomas,(3. 1971. Met. Trans. 2:2373 112. Frank, F. C. 1953. Acta Met. 1:15
97. Shimuzu, K., Nishiyama, Z. 1972. Met. ll3. Bilby, B. A, 1953. Phil. Mag. 44:782
Trans. 3:1055 114. Schoen, F. S., Owen,W. S. 1971. Met.
98. Tamura, I., Yoshimura, H., Ibaraki, Trans. 2:2431

M., Tagaya, M. 1964. Trans. Jap. Inst. 115. Proc. Int. Conf. Struct. Properties Grain
Metals 5:47 Boundaries, Interfaces, Yorktown
99. Kelly, P. M., Nutting, J. 1960. Proc. Heights, NewYork. 1972. Surface Sci.
Roy. Soc. A 259:45 Vol. 31
100. Speich, G. R., Swarm, P. R. 1965. J. 116. Zener, C. 1948. Elasticity and Anelas-
Iron Steel Inst. London203:480 ticity of Metals, Ch. IV. Illinois: Univ.
101. Shimuzu, K., Oka, K., Wayman,C. M. Chicago Press
1970. Acta Met. 18:1025 117. Sandrock, G. D., Perkins, A. J., Hehe-
102. Kelly, P. M., Nutting, J. 1959. J. 1ton mann, R. F. 1971. Met. Trans. 2:2769
Steel lnst. London 192:246 118. Honeycombe, R. W. K., Piekering, F.
103. See Ref. 102, 1961. 197:199 B. 1972. Met. Trans. 3:1099
104. Speich, G. R., Warlimont, H. 1968. J. ll9. Aaronson, H. I. 1969. Inst. Metals
Iron Steel Inst. london 206:385 Monogr. 33:270
105. Das, S. K., Thomas, G. 1970. Met. 120. Laird, C., Aaronson, H. I. 1969. Acta
Trans. 1:325, 2009 Met. 17:505
106. Oka, M., Wayman, C. M. 1969. Am. 121. Liu, Y. C., Aaronson, H. I. 1970. Acta
Soc. Metals Trans. 62:370 Met. 18:845

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Annual Reviews

METALS AND ALLOYS 8546

Glyn Meyrick and Gordon W. Powell

Understanding a phase transformation involves an appreciation of the reasons

328 MEYRICK ¯ POWELL

is assumed to be effected by the uncoordinated, random jumps of individual

appropriate term in the sense that it is descriptive of the relatively large

PHASE TRANSFORMATIONSIN METALS AND ALLOYS 329

too rigidly. It is to be emphasizedthat a phase transition can involve a structural

experimental observations the current knowledge of the morphological and

various modes of transformation will be considered under one of three broad

330 MEYRICK & POWELL

Figure I Microstructure of high punty iron quenched at approximately(a) 800"C/sec and

PHASE TRANSFORMATIONSIN METALS AND ALLOYS 331

Bharucha et al (17) by the use of thermionic emission microscopy. The geometry

of the massive boundaries, and internal structure of the massive phase.

332 MEYRICK L POWELL

Figure 3 Austenite (light)-to-ferrite (dark) transformation in high purity iron. Elapsed

Figure 4 Morphology of the a, phase in a Cu-37.8 at.% Zn alloy.

PHASE TRANSFORMATIONSIN METALS AND ALLOYS 333

Massalski (21), provides a mechanism for the formation of ledges. When

interface geometry shown in Figure 7. The precise mechanism by which the

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Figure 6 Ledge growth of the 8, phase in a Cu-22.8 at.%Ga alloy.

PHASE TRANSFORMATIONSIN METALS AND ALLOYS 335

one another. The decomposition of Fe-C austenite to pearlite is a more complex

336 MEYRICK & POWELL

PHASE TRANSFORMATIONS IN METALS AND ALLOYS 337

Figure 8 Early stage of cellular growth Figure 9 Fully-developed cells in a Pb-

Figure 10 Development of cooperative growth by the Tu-Turnbull mechanism (after Tu

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events producing cooperative growth is beautifully illustrated by the transmis-

depleted a phase. The Fournelle-Clark mechanism for the development of

PHASE TRANSFORMATIONS IN METALS A N D ALLOYS 339

Development of cooperative growth by the Fournelle-Clark mechanism (after

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According to Zener’s theory (38) of the cellular reaction, the intedamellar

the interlamellar spacing whereas the last increases the spacing.

In the case of pearlite the spacing is decreased by the branching mechanism

Although this equation has the form associated with volume-diffusion-controlled

(a) (b) (c) (d)

Figure13 Formationof pearlite froma ferrite, allotriomorph.

Figure 14 Mechanismsby which the in- Figure 15 Nonequilibrium solvus lines

PHASE TRANSFORMATIONSIN METALS AND ALLOYS 343

have a significant effect on the morphological development of the precipitate

enhanced diffusivity at such boundaries. Whylow angle boundaries should

required to form a semieoherent matrix-product interface.

Figure 16 Variation of precipitate morphologywith grain misorientation R. X, Y, and Z

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Dislocations also are favored nucleation sites at low degrees of undercooling.

Mathematical analyses of the growth of allotriomorphs are based normally on

PHASE TRANSFORMATIONSIN METALS AND ALLOYS 345

Figure 18 Thea + O’ to a + 0 transformationin a Cu-Alalloy (after Laird &Aaronson,

growth the lengthening of ferrite allotriomorphs takes place at a constant rate

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is actually the case, then the rate of thickening of Widmanstattenferrite should

research on this transformation.

by the equilibrium second phase. In an AI-4 wt.% Cu alloy the precipitation

PHASE TRANSFORMATIONSIN METALS AND ALLOYS 347

correct and sufficient definition of a martensitic transformation.

martensitic transformation is related to its parent through a habit plane and

348 MEYRICK & POWELL

system to follow only a single path of transformation somehybridization is to be