j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 4 : 3 1 3 4 e3 1 3 9

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Short Communication

Precipitation of dispersoids in AleMgeSi alloys

with Cu addition

Fang-Zhen Liu a,b,d, Jian Qin a,b,*, Zhen Li a,b, Cheng-Bin Yu a,b,d,
Xing Zhu c, Hiromi Nagaumi a,b,***, Bo Zhang d
a
School of Iron and Steel, Soochow University, Suzhou, 215021, China
b
High-Performance Metal Structural Materials Research Institute, Soochow University, Suzhou, 215021, China
c
Analysis and Testing Center, Soochow University, Suzhou, 215123, China
d
Shandong Weiqiao Aluminum &Electricity Co., Ltd, Binzhou, 256200, China

article info abstract

Article history: Nanoscale a-Al(FeMn)Si dispersoids in Al alloys play a vital role in improving the recrys-
Received 4 June 2021 tallization resistance and mechanical properties of alloys at elevated temperatures. This
Accepted 25 August 2021 study investigates the influence of Cu on the precipitation behavior of a-dispersoids in Al
Available online 30 August 2021 eMgeSi alloys during heat treatment at 500
C. a-dispersoids in an alloy without Cu
addition had rod- or plate-like morphologies. The addition of Cu effectively inhibits the
Keywords: precipitation of a-dispersoids through the formation of fine spherical dispersoids, resulting
AleMgeSi alloy enhanced mechanical properties of the alloy at elevated temperatures. Evidence from
Crystal structure high-resolution transmission electron microscopy demonstrated that the rod- or plate-like
a-Dispersoids structures have simple cubic structures, whereas the spherical a-dispersoids are coherent
Elevated temperature mechanical with the Al matrix along the [101] zone axis of Al, resulting in finer dispersoids, higher
properties thermal stability, and lower coarsening rates. However, its crystal structure requires
Precipitation further investigation.
© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

AleMgeSi alloys [1e5], which are promising candidates for

1. Introduction
AleMgeSi alloys have garnered significant attention in the
transportation industry because of the pressing need to
reduce carbon emissions. AleMgeSi alloys are required to
have moderate strength at elevated temperatures for a long
duration to maintain overall structural stability and ensure
sufficient escape time in case of fire hazards. a-Al(FeMn)Si
dispersoids precipitate during homogenized heat treatment of
elevated-temperature strengthening applications because of
their excellent thermal stability. However, owing to the rela-
tively high temperature (550
C) of homogenization, a-dis-
persoids coarsen easily [6].
Numerous studies have been conducted to determine the
improvement mechanism of the dispersion strengthening
caused by a-dispersoid and high-temperature thermal stabil-
ity properties [7]. The addition of transition metal elements,
such as Mn and Cr, can effectively promote precipitation and

* Corresponding author.
*** Corresponding author.
E-mail addresses: jian.qin@uqac.ca (J. Qin), zhanghai888jp@suda.edu.cn (H. Nagaumi).
https://doi.org/10.1016/j.jmrt.2021.08.123
2238-7854/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 4 : 3 1 3 4 e3 1 3 9
increase the number density of dispersoids [8]. In addition, the
low diffusion rates of Mn and Cr ensure the thermal stability
of dispersoids at high temperatures [9].
Numerous studies [10e20] propose that better thermal
stability can be achieved in Al and Ni alloys by reducing the
lattice mismatch between the precipitates and matrix. Fine
et al. [14] observed that particles with a lower lattice mismatch
present lower interfacial energy. In Ostwald ripening, the
growth of larger particles that consume smaller particles is
driven by a reduction in the total interfacial free energy. Thus,
a lower interfacial energy is desirable for the particles to resist
coarsening [14]. The transformation from semi-coherence to
coherence effectively reduces the lattice mismatch, thereby
reducing the interfacial energy and elastic strain energy, and
resulting in an improvement in thermal stability and me-
chanical properties of the particles [16]. Therefore, adjusting
the crystal structure is a promising approach to simulta-
neously improve the a-dispersoid thermal stability and alloy
mechanical properties.
However, extensive research on the crystal structure of
dispersoids in AleMgeSi alloys has not been conducted. In
this study, AleMgeSi alloys with and without 0.6 wt% Cu
addition were heat-treated to investigate precipitation
behavior and microstructural evolution of a-dispersoids and
the role of Cu in the precipitation behavior.
2. Experimental
The alloys with compositions of Ale0.82Mge1.07Sie0.71Mne
0.19Cre0.05Fe (0Cu alloy) and Ale0.84Mge1.04Sie0.58Cue
0.71Mne0.2Cre0.05Fe (0.6Cu alloy) used in this study were
cast to a copper mold of 24  100  200 mm3. The cast ingots
were heated to 500
C at a heating rate of 180
C/h and held for
24 h. The homogenized samples were thereafter dipped in
water to analyze the evolution of a-dispersoids. The alloys
homogenized for 10 h were hot forged from 20 to 4 mm
thickness with a reduction ratio of 80% after a single pass at
500
C on a laboratory-scale forging machine. The forged
samples were solution-treated at 560
C for 1 h and dipped in
water at ambient temperature levels. To evaluate the me-
chanical properties of the alloys at elevated temperatures, the
solution-treated specimens were annealed at 300
C for 100 h
and thereafter tensiled at 300
C using a universal mechanical
testing machine according to the ASTM E21 standard. The
Fig. 1 e Microhardness evolution of sample annealing (a) at 300
C for varying time durations and tensile properties (b) at
300
C after annealing for 100 h.
3135
thermal stability of the alloys was measured through micro-
hardness tests at ambient temperature levels, which were
performed on a Buehler Wilson microhardness test machine
with a load of 200 g and a dwell time of 20 s on polished
samples. Optical microscopy (OM) was performed to verify the
distribution and precipitation of the dispersoid zone. Trans-
mission electron microscopy (TEM), high-resolution TEM
(HRTEM), and energy-dispersive X-ray spectroscopy (EDX)
were performed at 200 kV to characterize the morphology,
size, and chemistry of the dispersoids.
3. Results and discussion
Fig. 1 shows the evolution of microhardness after annealing at
300
C for different holding times (Fig. 1(a)) and tensile prop-
erties at the same temperature after soaking for 100h (Fig. 1(b))
of 0Cu and 0.6Cu alloys. In the initial stage, the microhardness
of both alloys decreased rapidly during annealing for 20 h and
thereafter became stable with prolonged annealing. During
the entire annealing process, the 0.6Cu alloy always had a
higher microhardness than that of the 0Cu alloy. The me-
chanical properties of 6xxx alloys deteriorated rapidly
because of overcoarsening of Mg2Si or Q [21,22]. Therefore, the
contribution of the precipitates to the strength is insignificant.
The difference in microhardness of both alloys in the stable
stage was mainly due to a dispersoids, which were reported to
be thermally stable in a range of 200e350
C [22]. After
annealing at 300
C for 100 h, the yield strengths of the 0Cu
and 0.6Cu alloys at annealing temperature were 26 and
54 MPa, respectively. According to the Orowan strengthening
mechanism [23], a dispersoids in the 0.6Cu alloy should have a
higher volume fraction or finer size than those of the 0Cu
alloy.
To reveal the precipitation and distribution of a-disper-
soids in both alloys, which were heated at 500
C for 24 h, OM
images taken from deeply etched samples were utilized. The
a-dispersoids represented by etching pits are shown in Fig. 2 (a
& b). The a-dispersoids precipitated in the 0Cu alloy (Fig. 2(a))
were characteristic of large and dendritic areas with a greyer
color than that of the 0.6Cu alloy (Fig. 2(b)). This indicates that
the 0Cu alloy has a higher fraction or larger size of a-disper-
soids. Hence, the area fraction of a-dispersoids in the 0.6Cu
alloy is lesser than that of the 0Cu alloy because the etching
pits are too fine to be observed through OM.
3136 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 4 : 3 1 3 4 e3 1 3 9

Fig. 2 e OM images of a-dispersoids precipitated in (a) 0Cu and (b) 0.6Cu alloys soaked at 500
C for 24 h.

TEM was employed to further observe the morphology and
evolution of the a-dispersoids. The TEM micrographs of a-
dispersoids in 0Cu and 0.6Cu alloys that were heated to 500
C
(Fig. 3(a & d)) and held for 4 h (Fig. 3(b & e)) and 24 h (Fig. 3(c &
f)) are shown in Fig. 3, respectively. The a-dispersoids in the
0Cu alloy (Fig. 3(a)) were characterized by a rod- or plate-like
morphology and a small number of spherical shapes. Mean-
while, most of the a-dispersoids in the 0.6Cu alloy have a
spherical morphology (Fig. 3(d)). Compared to the 0Cu alloy,
the a-dispersoids precipitated in the 0.6Cu alloy were clearly
finer. When the soaking time of the homogenization heat
treatment increased to 24 h, the size of the a-dispersoids in
both alloys increased, whereas the number density decreased
(Fig. 3(c) and (f)). A large number of spherical a-dispersoids in
the 0.6Cu alloy (Fig. 3(f)) transformed into disc- or rod-like a-
dispersoids but were finer than those of the 0Cu alloy
(Fig. 3(c)).
The quantitative analysis of the evolution of a-dispersoids
in 0Cu and 0.6Cu alloys as a function of soaking time at 500
C
is shown in Fig. 4. The equivalent diameter of the a-disper-
soids in both alloys increased with prolonged soaking time.
Apparently, a-dispersoids in the 0.6Cu alloy have a finer size,
which is related to their crystal structure. As shown in
Fig. 4(b), the frequency of spherical a-dispersoids in the 0.6Cu
alloy is clearly higher than that of the 0Cu alloy and decreases
with increasing soaking time owing to transformation into
rod- or plate-like morphology. To analyze the coarsening of a-
dispersoids in detail, the sizes of rod- or plate-like and
spherical a-dispersoids in 0Cu and 0.6Cu alloys were
measured and are shown in Fig. 4(c & d), respectively. The a-
dispersoids in the 0Cu alloy exhibited similar coarsening rates
regardless of morphology. Meanwhile, the spherical a-dis-
persoids in the 0.6Cu alloy have a lower coarsening rate than
the rod- or plate-like a-dispersoids. Hence, the addition of Cu
not only refines a-dispersoids but also reduces their coars-
ening rate.
Numerous studies have shown that a-dispersoids have a
simple cubic (SC) or body-centered cubic structure. It is
interesting that spherical a-dispersoids in 0.6Cu alloy as
shown in Fig. 3(d) appear in “coffee-beam” form marked by
yellow arrows, which is known as AshbyeBrown contrast [24].
The contrast is caused by elastic distortions of the matrix near

Fig. 3 e TEM micrographs of a-dispersoids in 0Cu (a, b, c) and 0.6Cu (d, e, f) alloys heated to 500
C and soaked for 4 and 24 h,
respectively.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 4 : 3 1 3 4 e3 1 3 9 3137

Fig. 4 e Dispersoids equivalent diameter (a) and spherical dispersoids frequency statistics (b) of experimental alloys at
500
C with soaking time. Evolution of dispersoids’ size with different morphologies in 0Cu (c) and 0.6Cu (d) alloys at
500
C with soaking time.

the particles, indicating that a-dispersoids are coherent with
the Al matrix. Fig. 5(a) shows the selected area diffraction
pattern of a-dispersoids in the 0.6Cu alloy along the [110]Al
zone axis when it was heated to 500
C. The superlattice
pattern of the a-dispersoids is parallel to the Al matrix along
the (200)Al. TEM observations of the centered dark-field image
of a-dispersoids, which were recorded using the {100} super-
lattice reflections near the <011> direction under two-beam
diffraction conditions, and in situ bright field images are
shown in Fig. 5 (b) and (c), respectively. The results presented
in Fig. 5 (b) and (c) demonstrate that the a-dispersoids, which
are coherent with the Al matrix, are spherical.
During soaking at 500
C, a-dispersoids in the 0.6Cu alloy
mainly have three morphologies, that is, rod-like, plate-like,
and spherical morphologies. HRTEM was employed to reveal
the high-magnification details and crystal structures of these

Fig. 5 e TEM micrographs analysis of a-dispersoids in 0.6Cu alloy heated to 500
C, and selected area diffraction pattern
along [110] zone axis and (200) plane of Al (a), in situ dark field (b) and bright field (c) images.
3138 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 4 : 3 1 3 4 e3 1 3 9

Fig. 6 e TEM micrographs of 0.6Cu alloy heated at 500
C for 1h (a). HRTEM micrographs obtained along the [100]Al zone axis:
(b) plate-like and [101]Al zone axis: (e) spherical a-dispersoids, corresponding diffraction pattern are shown in (c) and (f).
Indexing of the diffraction pattern shown in (c) and (f) are presented in (d) and (g), respectively. Line scan result of EDX
cross plate-like and spherical a-dispersoids (h).

forms of a-dispersoids based on fast Fourier transform (FFT)
diffractograms. The HRTEM and FFT diffractograms of a-dis-
persoids in the 0.6Cu alloy held at 500
C for 1 h, which have
various morphologies, are shown in Fig. 6(a). The results prove
that plate- and rod-like a-dispersoids have the same SC
structure. The HRTEM image and simulated FFT diffractogram
of plate-like a-dispersoids presented in the atomic plane are
shown in Fig. 6(bed). The orientation relationship between the
a-dispersoid and Al lattice was found to be (Fig. 6(c)): [100]Al//
[111]a. The HRTEM image and simulated FFT diffractogram of
spherical a-dispersoids are presented in Fig. 6(eeg), respec-
tively. The crystal structure of the spherical a-dispersoids is
coherent with the Al matrix along the [101] zone axis of Al, but
it needs to be further determined. This indicates that there is a
lower lattice mismatch between the spherical a-dispersoids
and a-Al matrix, thereby improving the thermal stability of
the spherical a-dispersoids. According to the EDX line scan-
ning result (Fig. 6 (h)), which scanned cross a plate-like dis-
persoids and spherical a-dispersoids, as shown in Fig. 6 (a),
both a-dispersoids were composed of Al, Mn, and Si, and there
was no significant variation in the Cu and Cr contents in the
dispersoids. Further analysis and characterization of spherical
a-dispersoids will be necessary to determine the effect of Cu
on the crystal structure of a-dispersoids.
4. Conclusion
The addition of Cu promotes the formation of spherical a-
dispersoids that are finer than rod- or plate-like a-dispersoids
in the alloy without Cu during homogenized heat treatment.
TEM and HRTEM analyses revealed that the rod- or plate-like
a-dispersoids had SC structures. Meanwhile, the spherical a-
dispersoids are coherent with the Al matrix along the [101]
zone axis of Al, which resulted in a higher thermal stability
and higher mechanical properties at high temperatures.
However, the crystal structure needs to be further examined.
The presence of a large number of spherical dispersoids in the
0.6Cu alloy led to improved mechanical properties at elevated
temperatures.
Declaration of Competing Interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
The authors acknowledge the financial support provided by
the National Natural Science Foundation of China (Grant No.
U1864209).
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