Scripta Materialia, Vol. 41, No. 11, pp.

12351240, 1999
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MORPHOLOGICAL INSTABILITIES IN Mg-7.7 at % Al

S. Matrejean1,2, M. Veron1,2, Y. Brechet1, G.R. Purdy2
1

LTPCM/ENSEEG, Domaine universitaire, 38402 Saint Martin dHe`res, France

McMaster University, 1080 Main Street West, L8S 4L7 Hamilton, Ontario, Canada
(Received August 24, 1998)
(Accepted August 26, 1998)

Introduction
The process of solid-solid discontinuous precipitation in the undercooled state is increasingly well
documented [1]. However, rather less is known about the stability of the discontinuous transformation
products against prolonged ageing or against dissolution on reheating. In this contribution, we report on
the response to ageing and to re-heating of the discontinuous precipitation product in an Mg-Al alloy.
This system was chosen in part because of the well-established kinetic and compositional data now
available for the discontinuous product, a lamellar composite of the solid solution phase (an h.c.p.
solution of Al in Mg), which grows at lower temperatures in concert with the intermediate compound
Mg17Al12 [2].

Microstructure and Experimental Procedure

The alloy chosen for this study was magnesium alloyed with 7.7 at % aluminum, with Mn as a main
impurity (480 ppm). After preparation at 650C under an argon SF6 atmosphere, the alloy was
extruded at 250C, yielding a 15 mm diameter rod [2]. All specimens were subsequently homogenized
at 420C for 48h then water-quenched. The microstructure at this stage consisted of a solid solution of
aluminum in magnesium, with a few well-separated, coarse, Al-Mn precipitates. This was the initial
condition for all subsequent heat treatments. Next, sections 2 mm in thickness were then cut and
subjected to various thermal cycles. A standard tube furnace was used for long heat treatments (t 3h),
whereas a salt bath was used for the shortest heat treatments (typically under one minute). Following
these isothermal treatments, all specimens were water-quenched.
Samples were prepared for optical observation (polished to 0.1 m alumina and chemically etched
5% hydrofluoric acid ethanol-). Thin foils were also prepared for transmission electron microscopy. Three mm discs were thinned to 150 m in kerosene, then dimpled with 6 m diamond paste to
70 m. Final thinning was achieved by ion milling using a cold stage (4 kV, 1 mA at an angle varying
from 12 to 10). Observations were performed on a JEOL 2010 FEG equipped with a scanning mode
(STEM) and a PHILIPS CM12 (used mainly for dark field imaging).
To describe the initial state of the materials, we will first focus on the two types of precipitation
reactions which are in kinetic competition in this alloy:
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Figure 1. The morphology of the discontinuous precipitation product. (a) The sample was solution treated at 420C before
isothermal transformation for 120 minutes at 212C. Note the varying orientation of the lamellae, indicating that a rigid habit
plane does not exist. (b) The isothermal tranformation was continued for 60h at 212C: no sign of spheroidization was observed.

Continuous precipitation which occurs by bulk diffusion. These precipitates have a well defined
orientation relationship with the matrix and a well-defined habit plane. They consist of disc-shaped
particles (Figure 3, top left), lying along the basal plane of the matrix [2].
Discontinuous precipitation which occurs via a cooperative process of diffusion in and precipitation
from an advancing grain boundary. In this case, the precipitates are lamellae oriented perpendicular
to the grain boundary (Figure 1) and the crystallographic relationships with the matrix are less
stringent [2].

Three types of heat treatments were employed.

Heat Treatment (1)This treatment was designed to lead to the completion of the discontinuous
precipitation process, and to any subsequent spheroidization of the product phase. Isothermal heat
treatments were carried out for 12 to 48 hours at temperatures of 200C, 220C, 240C and 260C.
Then the specimens were water quenched.
Heat Treatment (2)In order to separate morphological instabilities from other phenomena,
two-step heat treatments were performed. The first ageing (respectively 17h at 200C, 14h at 220C,
4h at 240C and 3h at 260C) was stopped when discontinuous precipitation fronts were just
stabilized. Subsequently a second ageing at 250C was performed during 10, 15 and 20 hours,
followed by water quenching.
Heat Treatment (3)This treatment was designed to promote discontinuous dissolution: the grain
boundary whose motion is responsible for discontinous precipitation is expected to move backwards,
dissolving the discontinuous precipitates, and leaving a single phase behind. Two-step ageing was
again used: specimens were first annealed for 60 h at 212C (in order to obtain complete discontinuous precipitation with no residual supersaturation [3]), then flash heated in a salt bath at 356C
for times less than 1 minute and water quenched.
Results and Discussion

As expected discontinuous precipitation was indeed obtained, as shown on Figure 1. However,

discontinuous coarsening was not observed, in contrast to the classical behavior of other discontinuous

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Figure 2. 212C, 60 h/Salt bath at 356C, 15s WQ. The mobile grain boundary and its direction of motion are indicated by
the curvature of the GB (arrows). The parent grain was a discontinuous precipitation cell, which has undergone spheroidization
(see Figure 1 (b) for comparison). (a) Clearly the microstructure has been modified by the GB motion (b) On the left, two
elongated precipitates appear to impede the grain boundary. On the right, we observe the result of dissolution and reprecipitation
at the grain boundary (see the surrounded precipitates at the GB that present a different contrast between the two sides of the GB).

precipitation systems (for example, Ni-In [4], Fe-Ni-Ti [5], Co-Si, Cu-In [6], Pb-Cd, Zn-Cd [7], Al-Zn
[8]). We note here that light-optical observation can be misleading. For example, a change in the
direction of propagation of the discontinuous front will modify the interlamellar distance, and this could
be misinterpreted as a result of discontinuous coarsening. In the same way, continuous precipitation,
because of its unidirectional appearance can be interpreted as discontinuous precipitation of small
spacing. Then the true discontinuous product could be taken as a result of discontinuous coarsening.
A classical type of morphological instability, spheroidization, was observed for heat treatments 1 (at
temperature higher than 220C) and 2. However spheroidization was observed only for those lamellae
resulting from discontinuous precipitation and not for continuously produced precipitates. We take the
stability of the continuous precipitates as an indication of the low energy of the habit plane, which will
yield equilibrium shapes that emphasize this interface [9]. The anisotropy of surface energy may then
prevent Rayleigh instability.
Heat treatment 3, at a temperature higher than dissolution temperature (355C), was designed to
yield to discontinuous dissolution (for example Cu-Cd [10], Pb-Sn [11], Al-Zn [12]). The expected
dissolution reaction, involving the reverse motion of the grain boundary, was never observed in these
experiments.
We did observe, however, that after a heat treatment of 30s at 356C, the microstructure had
undergone considerable coarsening, much greater than that expected from considerations of bulk
diffusion. Indeed it was clear from the TEM observations that substantial grain boundary motion had
occurred during the first 15 s of the flash heat treatment (see Figure 2). It is therefore considered highly
probable that grain boundary transport is responsible for many of the morphological changes accompanying flash heat-treatment, but it should be stressed that this discontinuous reaction is different from
discontinuous dissolution since the daughter phase, Mg17Al12 is either partially retained or
re-precipitated (Figure 2.(b)). Therefore we can suppose either that dissolution temperature (355C) was
not reached during the first 30s of the heat treatment, or that the driving force for dissolution was not
sufficient to have the reaction fully completed during such a short time.
Several types of behaviors are possible, involving cooperation of the moving grain boundary, the
solid solution phase and the daughter phase:

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Figure 3. 212C, 60 h/Salt bath at 356C, 15s. The grain boundary is moving from the bottom right to the top left into a
continuous precipitation cell. It envelops and bypasses the precipitate in the center. (a) Bright field image. (b) Dark field image,
the same precipitate orientation was observed on both sides of the GB.

At the grain boundary, dissolution of the precipitates in the parent phase can be observed (Figure 2).
Precipitation from the moving grain boundary can also occur either at the position immediately
adjacent to the location where the precipitates dissolve or at a position where the grain boundarys
curvature changes. The new precipitates are roughly spherical.
Some precipitates survive the passage of the grain boundary, in the sense that the grain boundary
either envelops or passes through them. The initial shape of the precipitates which survive is often
elongated with large facets (Figures 3 and 4).
In the parent phase, far from the moving grain boundary, we observe spheroidization and dissolution
of the discontinuous precipitation lamellae (Figure 2). We recall that precipitates originating from
continuous precipitation tend to be morphologically stable in the parent phase (Figure 4). In the

Figure 4. 212C, 60 h/Salt bath at 356C, 15s. The grain boundary is moving into a continuous precipitation cell as indicated by
the arrow. The precipitates in the parent grain do not spherodize. Those that survive the passage of the grain boundary are seen
to undergo spheroidization. The large precipitate is Al-Mn.

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daughter phase, the volume fraction of precipitates in the solid solution is less than that originally
precipitated i.e. partial dissolution has occurred. The surviving precipitates spherodize, regardless
of their continuous or discontinuous origin (Figures 2 and 4). Depending on the process which creates
them, the precipitates in the swept region either retain their original orientation (evidence that they
have been enveloped by the moving grain boundary), or are rotated with respect to their initial
orientation (which would result from passage of the boundary through the precipitates). These
differences are shown most clearly using dark field transmission electron microscopy (see Figure 3).
When they initially had a stable orientation -preventing spheroidization-, the passing through of the
moving grain boundary creates an unstable matching situation -which allows subsequent spheroidization.
Conclusions
1) The stability of the interfaces between the Mg-rich solid solution and the precipitated intermediate
phase Mg17Al12 is strongly dependent on the precipitation mode. Precipitates formed by a continuous mechanism possess a rigidly determined orientation relationship with the hexagonal parent
phase; their habit plane interfaces are of low energy and their shape and size are relatively stable.
In contrast, lamellae formed by discontinous precipitation are susceptible to morphological instabilities (spheroidization) on prolonged holding at the precipitation temperature.
2) For the expected subsequent reactions, neither discontinuous coarsening nor discontinuous dissolution was observed in the alloy composition investigated. Discontinuous coarsening often depends
on the presence of residual supersaturation, or segregation, in the product solid solution phase;
perhaps the conditions of the present experiment did not lead to sufficient driving force. It is more
surprising that none of the dissolution heat treatments gave rise to an expected discontinuous
dissolution process. One reason for this situation might be that the heating rate is too slow so that
before discontinuous dissolution can be reached, coarsening of precipitates along the grain boundary
has reduced the available driving force.
3) A rich variety of interactions among the participating phases and sweeping grain boundaries has
been observed, leading to the partial dissolution of the precipitates. Some precipitates formed by
continuous processes were found to be dissolved in the grain boundary, then reprecipitated with
other shapes. Other precipitates were bypassed by the boundary, and spherodized as their orientation
with the matrix was altered. It is clear that moving grain boundaries and their encounters with
precipitates play a complex and varied role in the processes of solution treatment.
Acknowledgment
The authors would like to thank Dr. J. K. Chen for his help in microscopy, and for useful discussions.
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