Scripta Materialia 54 (2006) 1853–1858

www.actamat-journals.com

Effect of manganese on grain refinement of Mg–Al based alloys

a,*
Peng Cao , Ma Qian b, David H. StJohn c

a
Department of Materials and Process Engineering, University of Waikato, Private Bag 3105, Hamilton, New Zealand
b
BCAST (Brunel Centre for Advanced Solidification Technology), Brunel University, Uxbridge Middlesex, West London, UB8 3PH, UK
c
CAST CRC, School of Engineering, University of Queensland, St Lucia, Q4072, Australia

Received 23 January 2006; received in revised form 12 February 2006; accepted 14 February 2006
Available online 9 March 2006

Abstract

Manganese is a grain refiner for high purity Mg–3%Al, Mg–6%Al, Mg–9%Al, and commercial AZ31 (Mg–3%Al–1%Zn) alloys when
introduced in the form of an Al–60%Mn master alloy splatter but the use of pure Mn flakes and ALTABTM Mn75 tablets shows no grain
refinement. Long time holding of the melt at 730 C leads to an increase in grain size. The mechanism is attributed to the presence of an
e-AlMn phase (hexagonal close-packed) in the master alloy splatter.
 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Magnesium alloys; Grain refining; Manganese; Splatter; AlMn intermetallics

1. Introduction
The rapid growth in consumption of magnesium alloys
in the automobile industry over the past two decades has
been mainly attributed to the development of high purity
AZ (Mg–Al–Zn) and AM (Mg–Al–Mn) series alloys intro-
duced in the 1980s [1–3]. As an iron remover, manganese
has played a critical role in this development [4]. On the
other hand, it has long been realised that the grain size of
Mg–Al alloys is associated with the presence of impurity
elements such as Fe, Mn, and/or C. Earlier work by Tiner
[5] on superheating of magnesium alloys showed that high
purity Mg–Al alloys with <0.02%Mn (hereafter in wt.%)
showed no appreciable superheating effect, while Mg–Al
alloys containing 0.19%Mn or more (up to 0.98%Mn) dem-
onstrated grain refinement. Subsequent work by Nelson [6]
on superheating of an Mg–9Al–2Zn–0.4Mn alloy, how-
ever, led to contradictory observations. Nelson found that
little grain refinement could be achieved by superheating
the melt unless the excessive manganese was removed from
*
Corresponding author. Tel.: +64 7 838 4466x6753; fax: +64 7 838
4835.
E-mail address: pengcao@waikato.ac.nz (P. Cao).
the alloy. Both Nelson and Tiner used MnCl2 as a manga-
nese additive.
Recently, Tamura and co-workers [7–10] revisited the
influence of minor impurity elements on the grain refine-
ment of high purity Mg–9%Al alloys (Fe < 0.001%;
Mn < 0.001%), using an Al–10%Mn master alloy as the
manganese additive. Contrary to Tiner’s but in agreement
with Nelson’s observations, Tamura et al. [7] found that
the average grain size of a chill bar sample increased pro-
gressively from about 40 lm to 160 lm with increasing
Mn content from less than 0.001 to 0.47%, where Fe was
kept as low as 0.002%. It was hence suggested that manga-
nese poisons the potency of the proposed Al–C–O nucle-
ants by forming quaternary Al–C–O–Mn intermetallics
[7]. However, scrutiny of Tamura et al.’s work [7,9] shows
that particles containing Al, Mn, Fe, O, and occasionally
Si, were also observed at the centre of some magnesium
grains. In a subsequent study on superheating of a com-
mercial AZ91E alloy, Tamura et al. reported that cross-
shaped Al–Mn(–Fe) particles were frequently observed
when the melt was rapidly cooled from the superheating
temperatures (e.g. 900 C) to the pouring temperature of
700 C [11], and suggested that these Al–Mn(–Fe) particles
are effective nucleation sites for magnesium grains. These

1359-6462/$ - see front matter  2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2006.02.020
1854 P. Cao et al. / Scripta Materialia 54 (2006) 1853–1858

conclusions seem to differ from those made before by the Mg-3% Al

same authors about the role of Mn in grain refinement. 400
Mg-6% Al
More recently, Byun et al. [12] studied the slurry formation Mg-9% Al

Grain size (μm)

process of AZ91 containing different Mn levels ranging
from 0.23% to 0.45%. Al8(Mn, Fe)5 particles were observed
in the resulting primary magnesium crystals. They thus
suggested that Al8(Mn, Fe)5 particles could act as nucle-
ation sites for primary magnesium grains in Mg–Al alloys
(the details of the Mn additive used were not reported),
and showed that a high Mn concentration favours the for-
mation of fine primary magnesium crystals because of the
generation of more Al8(Mn, Fe)5 particles in the melt.
This work aims to clarify whether Mn can be used as a
grain refiner for Mg–Al alloys, and the dependency of grain
refinement on the form of the Mn additive. The grain
refinement mechanism in relation to the effect of manga-
nese is discussed.
2. Experimental procedure
Four magnesium alloys, binary Mg–3%Al, Mg–6%Al
and Mg–9%Al made of sublimed high purity (99.98%) mag-
nesium and ultra-high purity aluminium (99.999%) ingots,
and a commercial AZ31 alloy were employed. In each
experiment, about 700 g of the alloy melt was prepared in
an aluminium titanite (AlTi2O5) crucible (diameter:
70 mm; height: 190 mm) at 730 C under a protective cover
gas (1.0% SF6 in 49% dry air and 50% CO2). The melt was
alloyed with manganese in the form of an Al–Mn master
alloy splatter with a nominal composition of 60 wt.%Mn
(according to the specification provided by the supplier,
the actual composition varies from 58 wt.% to 64 wt.%).
The amounts of addition of manganese were 0.1%, 0.2%,
0.5%, 0.8% and 1.0%, and the yield of manganese recovery
was approximately 30%. Cone samples were taken from the
top of the melt using a BN coated cone ladle (dimensions:
B20 · B30 · 25 mm3), after 5 min of manual stirring
following addition of the Al–60%Mn splatter. For compar-
ison, commercial purity electrolytic Mn flakes and
ALTABTM Mn75 tablets (London and Scandinavian Metal-
lurgical Ltd., England) were also used as Mn additives.
Samples of Mg–6%Al and Mg–9%Al were subjected to
an annealing treatment (420 C/2 h, air cooled) in order
to reveal the grain boundaries. In contrast, samples of
Mg–3%Al and AZ31 were simply examined in the as-cast
300
200
100
0.0 0.2 0.4 0.6 0.8 1.0
Amount of Mn addition (wt%)
Fig. 1. Grain size vs. Mn addition for high purity Mg–3%Al, Mg–6%Al
and Mg–9%Al alloys.
alloys conducted at 730 C. All three alloys show an initial
rapid decrease in grain size and further addition of manga-
nese results in little improvement. The significant drop in
the grain size of high purity Mg–3%Al alloys with a small
addition of manganese is attractive for grain refinement of
commercial AZ31 alloys. A series of tests were hence con-
ducted on a commercial AZ31 alloy. After remelting, a
total of 0.8%Mn was introduced to the melt at 730 C, in
four consecutive additions 0.1%, 0.1%, 0.3% and 0.3%.
As shown in Fig. 2, obvious grain refinement was achieved
by the addition of manganese. Fig. 3 presents an overview
of two etched samples of the AZ31 alloy corresponding to
the observations shown in Fig. 2.
It is interesting to note that the additions of manganese
in the two other forms, i.e. Mn flakes and ALTABTM Mn75
tablets, showed little grain refinement in all four alloys.
Fig. 4(a) and (b) shows two such examples. The grain size
data in Fig. 4, albeit scattered, clearly indicate that neither
ALTABTM Mn75 nor Mn flakes produced noticeable grain
refinement. On the other hand, the grain refinement effi-
ciency by the addition of Mn in the form of Al–60%Mn
master alloy splatter is reproducible and consistent. It is
therefore anticipated that, in the master alloy splatter there
700
600
Grain size (μm)

state because their grain structures can be easily distin- 500

guished using polarised light optical imaging. The average
grain size of each cone sample was measured from the cen- 400
tral region of a transverse section of the cone.
300

3. Results 200

3.1. Grain sizes of Mg–Al alloys treated with Mn 100

Base alloy 0.1% 0.2% 0.5% 0.8%
in various forms
Amount of Mn addition
Fig. 1 shows the results obtained from the grain-refining Fig. 2. Grain size vs. Mn addition for a commercial AZ31. The grain size
tests of high purity Mg–3%Al, Mg–6%Al and Mg–9%Al dropped from 650 to 270 lm after addition of 0.2%Mn.
 P. Cao et al. / Scripta Materialia 54 (2006) 1853–1858 1855

Fig. 3. Grain refinement of a commercial AZ31 alloy by the addition of extra manganese at 730 C: (a) after remelting, average grain size
(AGS) = 650 lm; and (b) after addition of 0.2%Mn following remelting, AGS = 270 lm.

550
AlMn phase (JCPDS 11-0416). Ellner [13] investigated
500 the Al–Mn phases in the compositional range of 35–
50 at.%Mn and detected only the Al8Mn5 phase in the
Grain size (μm)

450 splatter-cooled and water-quenched samples. The predom-

400
inant presence of the Al8Mn5 intermetallic evidenced in
Fig. 5 confirms Ellner’s finding [13] that the c phase (see
Alloy tested: Mg-3%Al
350 Additive: ALTABTM Mn75 the binary Al–Mn phase diagram in Fig. 6) is difficult to
retain by quenching to room temperature. However,
300 Fig. 5 shows that another type of high temperature phase,
250 the e-AlMn phase exists in the Al–60 wt.%Mn master alloy
0.0 0.5 1.0 1.5 2.0 splatter.
(a)
Amount of Mn addition
4. Discussion
240 Alloy tested: Mg-9%Al
220 Additive: pure Mn flake Although the XRD results indicate the presence of the e
phase, this phase is not predicted by the phase diagram in
Grain size (μm)

200
the Al–60%Mn master alloy splatter (Fig. 6). However,
180 there are three possibilities that could allow the e phase
160 to form during rapid cooling of the Al–60 wt.%Mn melt.
First, the actual composition of the splatter can be up to
140
64 wt.% according to the specification provided by the sup-
120 plier. The compositional variation in the splatter shifts the
100 composition into the L + e phase field (Fig. 6) and allows
0.00 0.05 0.10 0.15 0.20 0.25 0.30 the e phase to form as the primary phase. Second, the high
(b) cooling rate suppresses the formation of the c phase rela-
Amount of Mn addition, wt%
tive to the e phase, and shifts the peritectic transition
Fig. 4. Grain sizes of a high purity Mg–3%Al alloy treated with ALTABTM
Mn75 tablets (a) and a high purity Mg–9%Al alloy treated with
L + e ! c to a lower temperature. This will extend the
electrolytic Mn flakes (b), respectively. L + e phase field to a composition below 60 wt.%Mn and
allow the e phase to form as the primary phase. This type
of response to rapid cooling is feasible. For instance, work
exclusively exist some particles that could act as nucleants on metastable phase formation has shown that close
for magnesium grains after they are released into the melt. packed structures such as face-centred cubic and hexagonal
close-packed (hcp) can form more easily than more open
3.2. XRD examination of the Al–60%Mn master alloy crystal structures such as body-centred cubic structures
splatter [15,16]. Therefore, it is possible that formation of the c
phase (W type [13]) could be suppressed in relation to the
Fig. 5 shows the XRD spectrum of the Al–60 wt.%Mn e phase (hcp). Third, the Al–Mn phase diagram is still
master alloy splatter used in this study. Apart from the not well established, particularly with regard to those high
well-defined c2-Al8Mn5 reflections, some additional peaks temperature regions [13]. It is likely that the current phase
were detected, which are close to the reflections of an e- diagram may be slightly inaccurate as a few percentage
1856 P. Cao et al. / Scripta Materialia 54 (2006) 1853–1858

Experiment
AlMn, #11-0416
Al8Mn5, #32-0021

Intensity, a.u.

20 40 60 80 100
2θ, deg

Fig. 5. XRD spectrum of the Al–60 wt.%Mn master alloy splatter. Apart from the diffraction peaks from c2-Al8Mn5, some extra reflections are present
(indicated by arrows). Standard reflections of e-AlMn (JCPDS #11-0416) and c2-Al8Mn5 are represented by solid circle and hollow triangle dots,
respectively.

Fig. 6. A recently reassessed Al–Mn phase diagram [14]. The dashed line indicates the composition of the Al–60 wt.%Mn splatter.

shift in the L + e phase field would allow the e phase to
form as the primary phase.
The Al–60%Mn master alloy splatter thus contains two
intermetallic phases, the predominant c2-Al8Mn5 and the e
phase, particularly if the Al–Mn master alloy splatter has a
higher Mn content, e.g. 64 wt.%. From a crystallographic
point of view, the hcp e phase (a = 0.2697 nm) is more
likely to be a nucleant for magnesium grains than the
rhombohedric c2-Al8Mn5 (hR26, R 3m, a = 1.2630 nm
[17]), as e has a smaller lattice mismatch (4% misfit)
against Mg (hcp, a = 0.3200 nm) compared to c2-Al8Mn5
(20% misfit [18]). It is therefore hypothesised that the
hcp e phase acted as the nucleating particles for primary
magnesium grains, when the Al–60 wt.%Mn splatter was
introduced to the Mg–Al alloy melts.
However, it should be pointed out that the hcp e inter-
metallic phase is stable only at temperatures above
840 C. As such, these particles could transform to the
stable c2-Al8Mn5 subjected to a long time of holding at a
typical melting temperature (about 730 C). When this
occurs, the grain refining effect should fade away or even
disappear. In a previous study [20], we showed that a rela-
tively long time (e.g. 2 h) of holding at 730 C led to an
increase in the grain size of a high purity Mg–6%Al alloy
refined with 0.2%Mn. The results have been reproduced
in Fig. 7. These observations agree well with the findings
 P. Cao et al. / Scripta Materialia 54 (2006) 1853–1858
180
Grain size (μm)
140
100
60
20
Base alloy Mn addn 0.5 h 2h
Fig. 7. Grain sizes of high purity Mg–6%Al alloy samples: base alloy;
after addition of 0.2%Mn; after 0.5 h of holding following the addition of
0.2%Mn; and after a further 1.5 h of holding. The melt temperature was
fixed at 730 C and an aluminium titanite crucible was used. Data are from
Ref. [20].
made by Simensen et al. [19], who reported that after 2 h
of holding at 710 C the Mg–4%Al melt contained only
c2-Al8Mn5.
Similar observations have been reported by Nishino
et al. on the use of Al–4%B master alloy additives [21].
They found that different sources of the Al–4%B master
alloy produced different grain refining results when added
to an AZ91 alloy. For example, they found that the Al–
4%B master alloy containing AlB2 or b-AlB12 compounds
gave rise to significant grain refinement, while that contain-
ing a-AlB12 resulted in little grain refinement. The reason
was attributed to the different nature of the Al–B interme-
tallic compounds contained in different sources of the Al–
4%B master alloy. The dependency of grain refinement
on the types of the Mn additives could help explain rele-
vant phenomena reported in the literature. For instance,
Tamura et al. [7] reported the inhibiting effect of Mn on
the grain refinement of Mg–9%Al alloys using an Al–
10%Mn master alloy as the Mn additive, and ascribed
the inhibiting effect to the formation of a quaternary Al–
C–O–Mn phase. This could be due to the absence of potent
nucleant particles in the additive Al–10 wt.%Mn (i.e. Al–
5 at.%Mn). As evident from Fig. 6, the majority of interme-
tallic particles in the Al–10%Mn master alloy should be
Al6Mn, which has an orthorhombic structure (oC28,
Cmcm, a = 0.7555 nm) and is crystallographically a poor
nucleant for Mg grains.
Finally, it should be pointed out that Al–Mn alloys are
susceptible to metastable phase formation in the presence
of certain impurities. For example, it has been well docu-
mented that carbon promotes the formation of a metasta-
ble s phase in Mn–Al alloys in the vicinity of the
equiatomic composition [22,23]. The presence of iron and
other minor elements in commercial purity magnesium
alloys may change both the stability of the hcp e interme-
tallic phase as well as its crystallography under certain cir-
cumstances, thus affecting its refining ability. As well, it
should be noted that only a small volume fraction of the
e phase exists in the currently used Al–60 wt.%Mn splatter.
1857
A higher volume fraction of the e phase is expected in a
higher Mn content master alloy splatter. It has been shown
that the e phase can be retained to room temperature in a
Mn0.55Al0.433C0.017 alloy either by oil quenching or splat
cooling [22,23]. So, technically, there should be no problem
to produce an Al–Mn master alloy splatter that contains a
significant amount of the e phase. It is anticipated that such
a splatter should be able to produce more effective grain
refinement. In addition, since the high temperature c phase
(Fig. 6) has a favourable lattice parameter (a = 0.3063 nm),
it has the potential to be a useful nucleant for magnesium
grains. However there is evidence suggesting that it is very
difficult, if not impossible, to retain the c phase by quench-
ing [13].
5. Summary
Three types of Mn additive have been used to investigate
the influence of Mn on the grain refinement of high purity
Mg–3%Al, Mg–6%Al, Mg–9%Al and commercial AZ31
alloys. It is shown that the Al–60 wt.%Mn master alloy
splatter can give rise to obvious grain refinement in each
of the alloys examined. In contrast, the use of electrolytic
Mn flakes and ALTABTM Mn75 tablets shows little grain
refinement. XRD analytical results indicate that the Al–
60%Mn master alloy splatter contains an hcp e phase,
which is crystallographically favourable as a nucleant for
magnesium grains. The fine grain size obtained from the
use of the Al–60%Mn splatter increases after a long time
of holding at a given melt temperature. This is attributed
to the likely transformation from the hcp e phase to the
more stable c2-Al8Mn5, which is a less effective nucleant
for magnesium grains.
Acknowledgments
Mr. Paul Huysmans of the KBM Affilips, the Nether-
lands is acknowledged for the provision of the Al–
60%Mn master alloy splatter. The CAST CRC is thanked
for providing support for this research. The CAST CRC
was established under, and is supported in part by, the
Australian Government’s Cooperative Research Centres
scheme. MQ acknowledges the financial support from the
Royal Society.
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