Materials Letters 57 (2003) 3779 – 3783

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Correlation between grain boundary faceting–defaceting transition

and change of grain boundary properties with temperature
S.B. Lee*
Max-Planck-Institut für Metallforschung, Heisenbergstraße 3, D-70569 Stuttgart, Germany

Received 22 December 2002; received in revised form 15 January 2003; accepted 17 February 2003

Abstract

The temperature dependence of grain boundary (GB) properties (e.g., grain boundary tension, migration rate and sliding
rate) shows abrupt changes at certain temperatures, and such changes are accepted as evidence of a grain boundary phase
transition. It has been suggested that such changes in the temperature dependence are interpreted as being related to a phase
transition called the special – general grain boundary transition. However, they have not been well explained by the special –
general grain boundary transition model. In this paper, this transition model and the experimental results of changes of grain
boundary properties are briefly introduced, and the application of the model to the temperature dependence of grain properties is
critically reviewed. A correlation between grain boundary faceting – defaceting transition and the changes in the temperature
dependence of grain boundary properties are proposed.
D 2003 Elsevier Science B.V. All rights reserved.

Keywords: Grain boundary faceting – defaceting transition; Grain boundary properties; Special – general grain boundary transition

1. Introduction in the misorientation – temperature plot where there

Shvindlerman and Straumal [1] collected many
experimental results in many metallic and nonmetal-
lic systems showing extrema or abrupt changes in
the misorientation dependence of grain boundary
(GB) properties at various temperatures. They found
that misorientation coordinates of GBs showing such
singular properties largely coincide with those for
CSL boundaries specified by A value [1]. The
special boundaries exist in certain, finite ranges of
angles around CSL misorientations and temperatures
* Tel.: +49-711-6893650; fax: +49-711-6893522.
E-mail address: bolee@hrem.mpi-stuttgart.mpg.de (S.B. Lee).
are phase boundaries between the special GB and the
general GB (the special –general GB transition) [1].
The transition temperatures of the special – general
GB transition decrease with the increase in a devia-
tion from a CSL misorientation angle. When the
misorientation angles of GBs are deviated from the
exact CSL misorientation angles, the secondary GB
dislocations (SGBDs) are introduced to accommo-
date such deviations and to preserve the CSL boun-
dary configurations [2,3]. The SGBDs disappear with
the increase in a deviation from CSL misorientation
angles at a given temperature [4] or with the increase
of temperature at a fixed misorientation angle [5].
From these results, Shvindlerman and Straumal [1]
concluded that the special – general GB transition

0167-577X/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0167-577X(03)00178-2
3780 S.B. Lee / Materials Letters 57 (2003) 3779–3783
could be explained by the disappearance of the
SGBDs.
Changes in the temperature dependence of GB
properties (e.g., GB tension, sliding rate and migra-
tion rate) observed by several researchers [6– 9] have
been interpreted in terms of the special – general
transition model [1,10]. Maksimova et al. [6] inves-
tigated the temperature dependence of GB tension of
[001] tilt boundaries with misorientation angles
between 25.5j and 30j (around 28.2j) (A17) in Sn
in a temperature range between 0.85Tm and Tm,
where Tm is the melting temperature of Sn. In this
study, migration rate of [001] tilt boundaries with
misorientation angles between 26j and 29.5j was
also examined in a temperature range between
0.94Tm and 0.98Tm. Out of the examined GBs, those
with A17 and near-A17 misorientation angles show
abrupt changes in the slope (slope discontinuity) at
certain temperatures (henceforth, called transition
temperature) in the temperature dependence of GB
tension. They also show abrupt changes of migration
rate at certain transition temperatures. The transition
temperatures for the migration rate change coincide
with those at which the relative GB tension shows
the slope discontinuities. The transition temperature
in the temperature dependence of GB tension and
migration rate is 0.97Tm at the misorientation angle
of 28.2j (A17) and it shows a tendency to decrease
with the increase in a deviation of the misorientation
angle from A17 [6]. From this result, they supposed
that the temperature dependence of GB tension and
migration rate in the tilt boundaries with A17 and
near-A17 misorientation relationships of Sn could be
interpreted in terms of the special–general boundary
transition model proposed by Shvindlerman and
Straumal [1]. Maksimova et al. [6,7] found that the
temperature dependence of GB properties shows
characteristic features of a first-order phase transi-
tion.
Watanabe et al. [8] investigated the temperature
dependence of GB sliding rate for seven symmetric
h101̄0i tilt boundaries in Zn of 99.999 wt.% purity
and one tilt boundary of 99.99 wt.% purity. All
pure GBs (99.999 wt.%), except for 16.5j- and
52j-tilt boundaries, show slope discontinuities in
the temperature dependence at different tempera-
tures. From the temperature dependence plots, the
transition temperatures are summarized as 0.79Tm
for the 33j-tilt boundary, 0.69Tm for the 40j-tilt
boundary, 0.9Tm for the 54.2j-tilt boundary, 0.76Tm
for the 60j-tilt boundary and 0.75Tm for the 66j-tilt
boundary. The transition temperature of the impure
GB (the 40j-tilt boundary of 99.99 wt.% purity) is
0.75Tm, which is higher by 40 jC than that of the
pure 40j-tilt boundary. Lagarde and Biscondi [9]
also observed slope continuities in the temperature
dependence of sliding rate in 50j and 53j sym-
metric h001i tilt GBs in Cu; the transition temper-
atures are 0.53Tm for the 50j-tilt boundary and
0.82Tm for the 53j-tilt boundary. Rabkin et al.
[10] supposed that the slope discontinuities in the
temperature dependence of sliding rate [8] could be
explained in terms of the special –general GB tran-
sition.
The dislocation model for the special GB regions
[1 –3] is valid for explanation of the cusp formation
in misorientation dependence plots of GB tension
[6,11– 17]. Considering the elastic field energy and
core energy of the SGBD array, Balluffi et al. [2,3]
concluded that the elastic field energy exhibits a
cusp-like singularity at certain CSL misorientations.
Thus, the presence of the SGBD array in a GB can
be represented as evidence of the existence of low-
energy cusp minima in the GB tension –misorienta-
rion curve. (The misorientation dependence of GB
sliding rate [8,9,18] and of amount of GB sliding
[8,18,19] also shows cusps at special orientations.
For GB migration rate, the misorientation depend-
ence reveals maxima [20], and for the activation
enthalpy of GB migration rate, minima at special
misorientations [20,21]. However, it is not clear
whether the SGBD model can explain the singular-
ities in the misorientation dependence of GB migra-
tion rate and sliding. Such topics are outside the
scope of the paper and will not be discussed any-
more.)
Unlike the misorientation dependence, the temper-
ature dependence of GB properties shows a GB
phase transition at a fixed misorientation relation-
ship. At a fixed misorientation relationship, a phase
transition inducing the changes in the temperature
dependence can be that in which GB phases with
different inclinations (GB plane normal orientations)
are involved. Accordingly, the temperature depend-
ence will be independent of the misorientation
dependence. The conclusion is partly supported by
 S.B. Lee / Materials Letters 57 (2003) 3779–3783
the results of GB sliding of Watanabe et al. [8,18]
and Maksimova et al. [6]. The misorientation
dependence of GB sliding and sliding rate from this
study shows a cusp at a misorientation angle of
54.2j (near A9 [56.6j/h101̄0i]) above the transition
temperature (623 K [0.9Tm]) [8] corresponding to the
slope discontinuity in the temperature dependence.
Maksimova et al. [6] showed that cusps in the
misorientation dependence of GB tension at a misor-
ientation angle of A17 remain at the temperature
near the transition temperature (0.97Tm) of the spe-
cial – general GB transition corresponding to the A17
GB. If the slope discontinuities in the temperature
dependence of GB tension and sliding rate arise from
the special – general GB transition, the cusps in the
misorientation dependence will disappear above the
transition temperature [1], in contradiction to the
observations [6,8,18]. Another disagreement can be
found in the relationship between the transition
temperature and a deviation from a CSL misorienta-
tion angle. The special – general GB transition model
[1] predicts that the transition temperature will
decrease with the increase in a deviation from a
CSL misorientation angle. Different from the results
of Maksimova et al. [6,7], however, the results of
Watanabe et al. [8] show that the change of the
transition temperature with a deviation of the misor-
ientation angle away from A9 (56.6j/h101̄0i) is not
consistent with such expectation, although the tran-
sition temperature is the highest at 54.2j/h101̄0i near
A9 [8]. Thus, it has to be concluded that the
dislocation model of special – general boundary tran-
sition cannot be simply extended to the temperature
dependence of GB properties.
A representative example of a GB phase transition
in which GB phases with different GB inclinations
are involved is faceting –defaceting transition. Grain
boundary faceting – defaceting transition is a first-
order phase transition [22] and, therefore, can
explain the singularities [6 –9] observed in the tem-
perature dependence showing characteristic features
of a first-order phase transition. The aim of this
study is to call attention to a possible correlation
between the changes in the temperature dependence
of GB properties and GB faceting – defaceting tran-
sition.
In the next section, the concept of faceting –
defaceting transition and its experimental results
3781
are briefly introduced. Finally, the experimental re-
sults of the temperature dependence of GB proper-
ties are discussed in terms of faceting – defaceting
transition.
2. Queries and discussions
Thermodynamically, the equilibrium GB structure
should be considered for a grain embedded in
another grain. Grain boundary faceting can thus be
explained in terms of the equilibrium shape of the
embedded grain and its corresponding plot of GB
energy against the boundary normal orientation (g-
plot). At high temperatures, the equilibrium crystal
shape takes a nearly spherical shape because of
entropy. In this case, all GB plane normal orienta-
tions contribute to the shape, and GB faceting does
not occur. If a cusp is introduced at some orienta-
tions in the plot, this induces faceting into those
orientations in the equilibrium crystal shape and
concurrently causes GB plane orientations misor-
iented from the cusp orientations not to appear on
the shape. Those GB planes corresponding to for-
bidden orientations will be unstable and will be
faceted into allowed orientations in equilibrium,
maintaining its average GB normal orientation. The
GB structure can be either smoothly curved or
faceted. These two GB structures can be transformed
into each other.
The first direct observation of a faceting – defacet-
ing transition was reported by Hsieh and Balluffi
[23] in A3 asymmetric h111i tilt GBs in Al and Au,
and a A11 asymmetric boundaries in Al. They
observed the faceted structures in situ by hot-stage
electron microscopy in which the specimen was
heated and then cooled back to room temperature.
At low temperatures, this boundary is faceted. With
increasing temperature, the boundary become defac-
eted. As temperature decreases again, it becomes
faceted again. The defaceting transition temperatures
(Td) of A3 asymmetric h111i tilt GBs in Al and Au,
and a A11 asymmetric boundaries in Al are 0.54Tm,
0.85 – 0.89Tm and 0.96Tm, respectively. In a Cu
bicrystal, Bi induces GB faceting, but when Bi is
removed, the GB becomes smoothly curved [24].
Reintroduction of Bi causes the GB to facet rever-
sibly. Recently, Lee et al. [25] observed the facet-
3782 S.B. Lee / Materials Letters 57 (2003) 3779–3783
ing – defaceting transition in an asymmetric A5 [001]
SrTiO3 bicrystal GB of with an inclination angle of
about 0.1j away from the exact symmetric (310) GB
plane position. The bicrystal samples were made by
ultra-high-vacuum diffusion bonding and heat-treated
between 1100 and 1600 jC. Below 1300 jC, this
GB is faceted into the symmetric (310) and the
asymmetric (100)//(430) GB planes. At 1400 and
1500 jC, the GB is faceted into the symmetric (310)
and {210} planes. At 1600 jC, the GB becomes
defaceted. The Td of the GB was between 1500 and
1600 jC (0.75 –0.8Tm). Fig. 1a and b shows the
faceted GB heat-treated at 1400 jC and the defac-
eted GB at 1600 jC, respectively. The faceting –
defaceting transition behavior of the GB is inter-
preted in terms of the g-plot and its corresponding
GB Wulff shape [25].
Fig. 1. TEM images of the GBs heat treated at (a) 1400 jC for 3
days and (b) 1600 jC for 1 day.
Although Maksimova et al. [6,7], Watanabe et al.
[8] and Lagarde and Biscondi [9] implicitly assumed
the exact symmetric GB planes, the experimental
results of Lee et al. [25] shows that it is impossible
to prepare the exact symmetric bicrystalline GB, and
an asymmetric GB can undergo GB faceting –defa-
ceting transition. Since faceting – defaceting phase
transition is observed in a GB even with a very
small inclination from a symmetric GB plane posi-
tion [25], it is deduced that the singularities in the
temperature dependence of GB properties can be
related to faceting – defaceting transition. The deduc-
tion is indirectly supported by the observation that
the range of faceting – defaceting transition temper-
atures (0.54 – 0.96Tm) and that of the transition
temperatures in the temperature dependence of GB
properties (0.53 – 0.97Tm) overlap. Since faceting –
defaceting transition is affected by impurities as
shown in the case of Cu – Bi GB [24], the difference
in the transition temperature between the pure and
the impure 40jh101̄0i tilt boundaries in Zn shown in
the results of Watanabe et al. [8] is explained in
terms of the impurity effects on faceting – defaceting
transition.
3. Concluding remarks
The results of the temperature dependence of GB
tension, migration rate and sliding rate cannot be
simply interpreted in terms of the dislocation model
of the special – general GB transition model. The
model is likely to be limited to the misorientation
dependence of GB properties. In fact, it is not rea-
sonable to combine the misorientation dependence
behavior with the temperature dependence behavior
and explain them with the same transition model. The
observed singularities in the temperature dependence,
because occurring at GBs with fixed misorientation
relationships, are likely to be induced by a phase
transition in which GB phases with different GB
inclinations are involved. A possible candidate for
such a transition is GB faceting – defacetig transition.
This is a first-order phase transition and can explain
the singularities in the temperature dependence show-
ing features of a first-order phase transition. Of
course, more experiments and theoretical considera-
tions are required to support such a correlation.
 S.B. Lee / Materials Letters 57 (2003) 3779–3783
Acknowledgements
I thank Dr. Matous Mrovech for critical reading
and valuable comments.
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