materials

Article
Microstructure and Mechanical Properties of As-Aged
Mg-Zn-Sn-Mn-Al Alloys
Caihong Hou 1 , Zhisong Ye 1 , Fugang Qi 1, * , Liwei Lu 2 , Jia She 3 , Lifei Wang 4 , Xiaoping Ouyang 1 , Nie Zhao 1
and Jing Chen 1, *

1 School of Materials Science and Engineering, Xiangtan University, Xiangtan 411105, China
2 Hunan Provincial Key laboratory of High Efficiency and Precision Machining of Difficult-to-Cut Material,
Hunan University of Science and Technology, Xiangtan 411201, China
3 College of Materials Science and Engineering, Chongqing University, Chongqing 400045, China
4 Shanxi Key Laboratory of Advanced Magnesium-Based Materials, Taiyuan University of Technology,
Taiyuan 030024, China
* Correspondence: qifugang@xtu.edu.cn (F.Q.); sellenchenjing@aliyun.com (J.C.); Tel.: +86-156-1673-2585 (F.Q.)

Abstract: The microstructure and mechanical properties of as-aged Mg-6Zn-4Sn-1Mn-xAl (ZTM641-xAl,

x = 0, 0.2, 0.5, 1, 2, 3 and 4 wt.%) alloys are studied in this paper. In terms of microstructure, the results
reveal that the addition of Al mainly leads to the formation of the Al8 Mn5 , Al11 Mn4 , Al2 Mg5 Zn2 and
Mg32 (Al,Zn)49 phases. With increases in the addition of Al, the average grain size first decreases and
then increases, while the undissolved phases increase. The average grain size of the ZTM641-0.5Al
alloy is the smallest, and the single-aged and double-aged grain size is 14 µm and 12 µm, respectively.
As for mechanical properties, with increases in the Al element, the strength decreases, and the
elongation first increases and then decreases. The double-aged ZTM641-0.2Al alloy exhibits favorable
mechanical properties at room temperature, and the UTS, YS and elongation are 384 MPa, 360 MPa
and 9%, respectively. Further, the double-aged ZTM641-0.2Al alloy exhibits the comprehensive
mechanical properties at 150 ◦ C, that is, the UTS, YS and elongation are 212 MPa, 196 MPa and 29%,
respectively, which is about 45% higher than that of the elongation of ZTM641. The ZTM641-xAl
alloys exhibits mixed fracture at room temperature, and, with increases in the addition of Al, the
fracture mechanisms of alloys are mixed fracture, ductile fracture and mixed fracture at 200 ◦ C.
Citation: Hou, C.; Ye, Z.; Qi, F.; Lu, L.;
She, J.; Wang, L.; Ouyang, X.; Zhao,
Keywords: microstructure; mechanical properties; Mg-Zn-Sn-Mn-Al alloy; fracture mechanism;
N.; Chen, J. Microstructure and
aging treatment
Mechanical Properties of As-Aged
Mg-Zn-Sn-Mn-Al Alloys. Materials
2023, 16, 109. https://doi.org/
10.3390/ma16010109
1. Introduction
Academic Editors: Matthias Bönisch
and Jae Wung Bae
Magnesium alloys have many excellent properties, for instance, low density, good
casting performance and high recovery rate compared with other non-ferrous metals [1–5].
Received: 1 November 2022 However, their development is far inferior to other non-ferrous metals due to their poor
Revised: 8 December 2022 absolute strength and heat resistance [6]. Therefore, great interest has been directed towards
Accepted: 19 December 2022 improving the property of wrought Mg alloys [7,8].
Published: 22 December 2022
Among various alloy systems, the typical precipitation hardening of Mg-Zn wrought
alloys is widely reported. The precipitation sequence of Mg-Zn alloys during the aging
state is reported to be: SSSS → GP zones → β1 ’-MgZn2 → β2 ’-MgZn2 → β-MgZn [9,10].
Copyright: © 2022 by the authors.
Although the rod-like β1 ’ phase has an effective strengthening effect, the performances
Licensee MDPI, Basel, Switzerland. of Mg-Zn alloys are still unsatisfactory [11]. At present, alloying is seen as a common
This article is an open access article way to change the microstructure and performance of alloys. The Mg-Sn alloy is also
distributed under the terms and considered to be a precipitation hardening alloy, and the Mg2 Sn phase is an excellent
conditions of the Creative Commons precipitation hardening phase [12,13]. However, since the lath-shaped Mg2 Sn forms in
Attribution (CC BY) license (https:// the matrix and is parallel to the base plane, the precipitation hardening effect is obscure.
creativecommons.org/licenses/by/ Mendis et al. indicated that the strengthening effect of mixed Zn and Sn is better than
4.0/). that of single Sn or Zn, because the Zn element could improve the orientation relationship

Materials 2023, 16, 109. https://doi.org/10.3390/ma16010109 https://www.mdpi.com/journal/materials

Materials 2023, 16, 109 2 of 16

between Mg2 Sn and matrix, resulting in a great improvement of strength [14]. As for Al,
a kind of low-cost element, Oh-ishi et al. revealed that it could result in a change of the
morphology and distribution of the precipitates [10]. Zhang et al. identified that the Mg-Zn-
Al alloy produced three phases with Mg32 (Al,Zn)49 (τ), MgZn (ε) and a ternary icosahedral
structure, and the constituent was changed when the Zn and Al content changed [15].
Wan et al. studied the Mg-(8~12%)Zn-(2~6%)Al alloy, the results indicated that the creep
resistance is higher when the Zn/Al is between 2 and 3, and the ZA124 alloy shows the
best effects with a continuous network of τ phase structure [16]. Furthermore, recent
investigations have reported that the Mn element could obviously decrease the interfacial
energy of Mg-Zn alloy, then improve its strength [17]. Yin et al. found that the UTS, YS and
elongation of Mg-3Zn-Mn alloy were 315.5 MPa, 275.9 MPa and 10.5%, respectively [18].
In order to better meet the needs of industrial production, the research and develop-
ment of new alloys is particularly urgent. At present, there are several processing means
to improve the properties of Mg alloys: One is heat treatment, namely, the common so-
lution treatment and aging treatment [19]. The second is alloying, which is the addition
of small or trace elements to Mg alloys, to change the microstructure then improve the
properties of the alloy. Our team previously found that Mg-6Sn-4Zn-1Mn is an alloy with
excellent comprehensive properties, and the UTS, YS and elongation of double-aged alloys
are 390MPa, 378MPa and 4.16%, respectively [20]. The Al element is a good alloying
element, and studies show that in an appropriate amount it can refine grain and improve
the casting performance of the alloy atoms [21,22]; therefore, in this study, we developed
the Mg-6Sn-4Zn-1Mn-xAl alloy, and found that the Mg-Zn-Sn-Mn-xAl alloys before heat
treatment formed four new phases with the addition of the Al element, and the mechanical
performances were improved [23]. To further explore the potential properties of the Mg-
Zn-Sn-Mn-xAl alloy, it was heat treated with solution treatment and aging treatment. In
this paper, we mainly investigate the microstructure and properties of ZTM641-xAl alloy
after aging treatment.

2. Experimental Procedures
The experimental samples were successively melted, cast, homogenized and extrusion
treatment, these specific research and experimental results are presented in this paper [16].
Subsequently, the as-extruded alloys were solution-treated (the specific parameter was heating
at 430 ◦ C for 2h) and subjected to water cooling. Then, the single-aged and double-aged alloys
were treated, whose parameters were 180 ◦ C/12 h and 90 ◦ C/24 h + 180 ◦ C/8 h, respectively.
The as-aged alloys were tested for ultimate tensile strength (UTS), yield strength
(YS) and elongation at room temperature (150 ◦ C and 200 ◦ C). The test equipment was
the INSTRON 3369 electronic universal material testing machine, and the strain rate was
2 mm/min. To ensure accuracy, the stress–strain curve was tested five times, and the
mechanical properties of 0.2% YS, UTS and elongation were taken as the final value.
At the same time, the microstructure was also observed. The metallographic sample
was observed by an Olympus BX53M optical microscope (OM). The phase composition
was qualitatively analyzed by an U1tima IV X-ray diffractometer (XRD) using a Cu Kα
radiation, the angle range was 10~90◦ and the speed was 4◦ /min. The phase was quantita-
tively analyzed by a JSM-6360 scanning electron microscope (SEM) and an Oxford INCA
Energy 350 energy dispersive spectrometer (EDS). The higher resolution microstructure
was analyzed by FEI Tecnai G2 F30 transmission electron microscopy (TEM) equipped with
EDS detectors.

3. Results and Discussion

3.1. Microstructures of As-Aged ZTM641-xAl Alloys
The aging process follows the previous research results in this paper [24]: the single-
aged and double-aged treatments are 180 ◦ C/12 h and 90 ◦ C/24 h + 180 ◦ C/8 h, respectively.
Previous studies have found that there is little difference in the phase composition between
single-aged and double-aged alloys [25]. Thus, the XRD pattern of the single-aged ZTM641-
 3. Results and Discussion
3.1. Microstructures of As-Aged ZTM641-xAl Alloys
The aging process follows the previous research results in this paper [24]: the single-
aged and double-aged treatments are 180 °C/12 h and 90 °C/24 h + 180 °C/8 h, respectively.
Materials 2023, 16, 109 3 of 16
Previous studies have found that there is little difference in the phase composition be-
tween single-aged and double-aged alloys [25]. Thus, the XRD pattern of the single-aged
ZTM641-xAl (x = 0, 0.2, 0.5, 1, 2, 3 and 4%) alloys is summarized in Figure 1. From Figure
xAl (x = 0, 0.2, 0.5, 1, 2, 3 and 4%) alloys is summarized in Figure 1. From Figure 1a, we can
1a, we can see that the alloy has α-Mg, α-Mn, Mg2Sn and MgZn2 phases. When 0.2%Al is
see that the alloy has α-Mg, α-Mn, Mg2 Sn and MgZn2 phases. When 0.2%Al is added, Al
added,
elementAl element
does does not
not combine withcombine with other
other elements, and elements,
the alloy is and the alloy isby
still dominated still dominated
α-Mg,
by α-Mg, α-Mn, Mg
α-Mn, Mg2 Sn and MgZn2 phases. When the content of Al increases to 0.5%, the Al8 Mn0.5%,
2Sn and MgZn 2 phases. When the content of Al increases to 5
the
Al 8Mn
phase phase is
is5 formed, formed,
and andofthe
the content content further
Al increases of Al increases furtherthe(1%),
(1%), In addition, Mg32 In addition,
(Al,Zn) 49 the
Mg 32(Al,Zn)
phase and Al49 11 phase
Mn 5 and
phase Al Mn
appear
11 phase
among
5 appear
the among
alloys, and the
when alloys,
the Al and when
content the
increases Alto content
3%, the Al2to
increases Mg 5 Znthe
3%, 2 phase
Al2Mgappears in the alloy.
5Zn2 phase appears in the alloy.

Figure
Figure 1.1.XRD
XRDpatterns
patterns of the
of the single-aged
single-aged ZTM641-xAl
ZTM641-xAl alloys, alloys,
(a) x = 0,(a)
(b)xx==0,0.2,
(b)(c)xx==0.2,
0.5, (c)
(d) xx == 0.5,
1, (d) x =
1, (e) x = 2, (f) x = 3 and (g) x
(e) x = 2, (f) x = 3 and (g) x = 4. = 4.

Figures
Figures2–4 2–4show
show the microstructure
the microstructure andandaverage graingrain
average size, respectively, of the aged
size, respectively, of the aged
ZTM641-xAl alloys. The average grain size is measured by the
ZTM641-xAl alloys. The average grain size is measured by the Heyn transversal Heyn transversal method,method,
the details can be seen in the last paper [23]. Comparing Figures 2 and 3, it can be found
the details can be seen in the last paper [23]. Comparing Figures 2 and 3, it can be found
that the microstructure of single aging and double aging is similar. The double-aged alloys
that the microstructure of single aging and double aging is similar. The double-aged alloys
are subjected to gradient treatment, and the time is longer, then the secondary grain growth
are subjected
is more adequate toand
gradient treatment,
the average grain sizeand the time
is slightly is but
small, longer, then the
not obvious. Thesecondary
ZTM641 grain
growth is more adequate and the average grain size is slightly small,
alloy mainly comprises equiaxed crystals, but it is not uniform. The phases are basically but not obvious. The
ZTM641
distributed alloy
alongmainly comprises
the grain boundaries.equiaxed
When Al crystals,
elementbut it is not
is added, onuniform.
the one hand,The the
phases are
basically distributed along the grain boundaries. When Al element is added, on the one
volume fraction of phases slightly increases and the reveals that particles are mainly heat
stable Mg
hand, the2 Sn and Al-Mn
volume phases,
fraction as shown
of phases in the analysis
slightly results
increases andoftheFigure 1. Onthat
reveals the other
particles are
hand, when the Al content is 0.5%, the grains become more uniform,
mainly heat stable Mg2Sn and Al-Mn phases, as shown in the analysis results of and the sizes areFigure 1.
reduced to 12~14 µm (Figure 4). This can be ascribed to the evenly distributed Al content
On the other hand, when the Al content is 0.5%, the grains become more uniform, and the
and the numerous dispersed fine particles that hinder the movement of grain boundary [10].
sizes are reduced to 12~14 μm (Figure 4). This can be ascribed to the evenly distributed Al
As Al content further increases to 2%, the alloys gradually change towards the mixed crystal
content
structure,andandthethe numerous dispersed
grain size increases. fine particles
Compared thatparticles,
with finer hinder the this movement
is due to theof grain
boundary
increasing [10].
coarse Asphases
Al content
with afurther
weakerincreases
dispersion, to moreover,
2%, the alloys gradually change
the impediment to graintowards
the
growth is uneven, resulting in uneven grains and an increase in the average size finer
mixed crystal structure, and the grain size increases. Compared with particles,
[26]. In
order to further verify the residual alloy phase, a SEM and an EDS analysis were conducted.
 Materials 2022, 15, x FOR PEER REVIEW 4 of 17

this is due to the increasing coarse phases with a weaker dispersion, moreover, the im-
Materials 2023, 16, 109 pediment to grain growth is uneven, resulting in uneven grains and an increase 4in of the
16
average size [26]. In order to further verify the residual alloy phase, a SEM and an EDS
analysis were conducted.

Figure2.2.Optical
Figure Opticalmicrographs
micrographsofofthethesingle-aged
single-agedZTM641-xAl
ZTM641-xAl alloys,
alloys, (a)(a)
x=x =0,0,(b)
(b)x x= =0.2,
0.2,(c)
(c)x x==0.5,
0.5,
(d) x = 1, (e) x = 2, (f) x = 3 and (g) x = 4.
(d) x = 1, (e) x = 2, (f) x = 3 and (g) x = 4.

Figure 5 shows the backscatter electron (BSE) SEM microscope observations for the
single-aged ZTM641-xAl alloy. The ZTM641 alloy exhibits a favorable aging result, and the
remaining second phase comprises a bright Mg2 Sn and a grey MgZn2 phase [25]. After
adding Al content, on the one hand, it shows from Figure 5b that the dotted gray phase
at point A is Al8 Mn5 . As the Al content increased, Al8 Mn5 changes to Al11 Mn4 phase,
as shown at point B in Figure 5c, which is consistent with the report [27]. Additionally,
Dispersed fine phases are found at the grain boundaries, and with increases in the Al
element, the fine phase increases, and the phases are continuously distributed on grain
boundaries. Previous research has shown that these phases are Mg-Zn phases [28]. This
Materials 2023, 16, 109 5 of 16

indicates that, with the addition of a small amount of the Al element, the fine and dispersed
precipitated phases play the role of pinning the grain boundaries, which reduces the grain
size. However, as the Al content further increases, the bulk phases’—such as the Al-Mn
phases and Mg2 Sn phases—volume fractions increase, and the phases located on the
grain boundaries become continuous, resulting in an increase in the grain size, which is
consistent with above discussion. Furthermore, the specific morphology and type of these
Materials 2022, 15, x FOR PEER REVIEW
phases cannot be clearly observed by SEM due to its lower resolution. Therefore, the TEM 5 of 17

observation is adopted to identify the fine phases.

Figure3.3.Optical
Figure Opticalmicrographs
micrographs ofof the
the double-aged
double-aged ZTM641-xAl
ZTM641-xAl alloys,
alloys, (a)(a)
x =x 0,
= 0,
(b)(b)
x=x =0.2,
0.2,(c)(c)x x= =0.5,
0.5,
(d) x = 1, (e) x = 2, (f) x = 3 and (g) x = 4.
(d) x = 1, (e) x = 2, (f) x = 3 and (g) x = 4.
Materials 2022, 16,
Materials 2023, 15, 109
x FOR PEER REVIEW 66of
of 16
17

Figure 4. Average grain size of as-aged ZTM641-xAl alloys.

Figure 5 shows the backscatter electron (BSE) SEM microscope observations for the
single-aged ZTM641-xAl alloy. The ZTM641 alloy exhibits a favorable aging result, and
the remaining second phase comprises a bright Mg2Sn and a grey MgZn2 phase [25]. After
adding Al content, on the one hand, it shows from Figure 5b that the dotted gray phase at
point A is Al8Mn5. As the Al content increased, Al8Mn5 changes to Al11Mn4 phase, as
shown at point B in Figure 5c, which is consistent with the report [27]. Additionally, Dis-
persed fine phases are found at the grain boundaries, and with increases in the Al element,
the fine phase increases, and the phases are continuously distributed on grain boundaries.
Previous research has shown that these phases are Mg-Zn phases [28]. This indicates that,
with the addition of a small amount of the Al element, the fine and dispersed precipitated
phases play the role of pinning the grain boundaries, which reduces the grain size. How-
ever, as the Al content further increases, the bulk phases’—such as the Al-Mn phases and
Mg2Sn phases—volume fractions increase, and the phases located on the grain boundaries
become continuous, resulting in an increase in the grain size, which is consistent with
above discussion. Furthermore, the specific morphology and type of these phases cannot
be clearly
Figure 4.
observed
4. Average
by SEM
grain size
size of
due toZTM641-xAl
of as-aged
its lower resolution.
as-aged ZTM641-xAl alloys.
Therefore, the TEM observation
Figure
is adoptedAverage grain
to identify the fine phases. alloys.

Figure 5 shows the backscatter electron (BSE) SEM microscope observations for the
single-aged ZTM641-xAl alloy. The ZTM641 alloy exhibits a favorable aging result, and
the remaining second phase comprises a bright Mg2Sn and a grey MgZn2 phase [25]. After
adding Al content, on the one hand, it shows from Figure 5b that the dotted gray phase at
point A is Al8Mn5. As the Al content increased, Al8Mn5 changes to Al11Mn4 phase, as
shown at point B in Figure 5c, which is consistent with the report [27]. Additionally, Dis-
persed fine phases are found at the grain boundaries, and with increases in the Al element,
the fine phase increases, and the phases are continuously distributed on grain boundaries.
Previous research has shown that these phases are Mg-Zn phases [28]. This indicates that,
with the addition of a small amount of the Al element, the fine and dispersed precipitated
phases play the role of pinning the grain boundaries, which reduces the grain size. How-
ever, as the Al content further increases, the bulk phases’—such as the Al-Mn phases and
Mg2Sn phases—volume fractions increase, and the phases located on the grain boundaries
become continuous, resulting in an increase in the grain size, which is consistent with
above discussion. Furthermore, the specific morphology and type of these phases cannot
be clearly
Figure observed
5. BSE-SEM by SEM due
micrographs of thetosingle-aged
its lower resolution.
ZTM641-xAlTherefore,
alloys, (a) x the
= 0, TEM
(b) x =observation
0.5, (c) x = 2,
is adopted to identify the fine phases.
(d–f) corresponding EDS results of the points indicated in (b,c).

Figures 6 and 7 show the TEM images of single-aged ZTM641-1Al alloy. According to
− −
the incident beam parallel to [ 12 16]α-Mg , Figure 6a shows the BF-TEM images subjected to
single-aged treatment (180 ◦ C/12 h). Three precipitates are dispersed in single-aged alloy:
rod-shaped, disc-shaped and irregular phases. Among them, the rod-shaped precipitates
account for the vast majority, and it can be obviously observed that rod-shaped precipitates
have an obvious and consistent growth relationship between the matrix. It is reported
that the precipitate perpendicular to the rod-shaped phase is the disc-shaped β2 ’-MgZn2
phase, this lays on the base surface, and its strengthening effect is much weaker than that
of the rod-shaped phase [29]. In order to further verify the types of these fine phases, an
EDS energy spectrum analysis is carried out. Based on the EDS data at point D in Figure 7,
the rod-shaped precipitates are identified as β1 ’-MgZn2 , and the EDS results at point A
in Figure 6 and E in Figure 7 show that these precipitated phases perpendicular to the
β1 ’are β2 ’, and point B in Figure 6 is irregular shaped Mg2 Sn phase, which is consistent
well with the above results. In addition, a micron-sized Al-Mn phase is also observed
 ported that the precipitate perpendicular to the rod-shaped phase is the disc-shaped β2’-
MgZn2 phase, this lays on the base surface, and its strengthening effect is much weaker
than that of the rod-shaped phase [29]. In order to further verify the types of these fine
phases, an EDS energy spectrum analysis is carried out. Based on the EDS data at point D
Materials 2023, 16, 109
in Figure 7, the rod-shaped precipitates are identified as β1’-MgZn2, and the EDS results 7 of 16
at point A in Figure 6 and E in Figure 7 show that these precipitated phases perpendicular
to the β1’are β2’, and point B in Figure 6 is irregular shaped Mg2Sn phase, which is con-
sistent well with the above results. In addition, a micron-sized Al-Mn phase is also ob-
in Figure
served 6e. This
in Figure is considered
6e. This a residual
is considered a residualphase,
phase,which isundissolved
which is undissolved in in
thethe matrix
matrix
during
duringsolid
solid solution stage. The
solution stage. Theββ1’1perpendicular
’ perpendiculartoto basal
basal plane
plane is the
is the main
main strengthening
strengthening
phase,
phase, which
which can
can effectively pinthe
effectively pin thegrain
grainboundaries
boundariesduring
during alloy
alloy deformation
deformation process
process
and prevent dislocation slipping
and prevent dislocation slipping [30].[30].

Figure6.6. TEM
Figure TEM micrographs
micrographs of ofthe
thesingle-aged
single-agedZTM641-1Al
ZTM641-1Alalloy, (a)(a)
alloy, Bright-field (BF)(BF)
Bright-field TEM image,
TEM image,
taken along the −121 −6 α-Mg zone axis, (b) HRTEM image of “T” phase (c–e) HAADF-STEM image,
taken
inset: along
Materials 2022, 15, x FOR PEER REVIEW
the [ 12 16]
corresponding EDS zoneofaxis,
results
α-Mg (b) HRTEM image of “T” phase (c–e) HAADF-STEM
the points. 8 of 17
image,
inset: corresponding EDS results of the points.

Figure 7. TEM micrographs of the single-aged ZTM641-1Al alloy, (a) Diffraction spots of the matrix,
Figure 7. TEM micrographs
(b) HAADF-STEM, taken alongof
thethe12single-aged ZTM641-1Al
13 α-Mg zone axis, alloy, (a) Diffraction
inset: corresponding spots
EDS results of the of the matrix,
− −
points
(b) (c) HRTEM image
HAADF-STEM, of the
taken β1’-MgZn
along the 2[phase
12 13]and (d) corresponding FFT pattern of (c).
α-Mg zone axis, inset: corresponding EDS results of the
points (c) HRTEM image of the β1 ’-MgZn2 phase and (d) corresponding FFT pattern of (c).
According to the incident beam parallel to 1213 α-Mg, Figure 7b shows that a small
amount of Sn is found. When the solute Sn atoms are concentrated at one end of β1’, the
heterogeneous nucleation effect is greatly reduced, and due to the increased nucleation
energy barrier, the Mg2Sn phase is easy to nucleate at one end of the rod to form a “T”
shaped phase, resulting in the a shorter length than that of ordinary β1’ [31,32], which is
consistent with the result in Figure 6b. Figure 7c is the HRTEM of β1’ in the single-aged
Materials 2023, 16, 109 8 of 16

− −
According to the incident beam parallel to [ 12 13]α-Mg , Figure 7b shows that a small
amount of Sn is found. When the solute Sn atoms are concentrated at one end of β1 ’, the
heterogeneous nucleation effect is greatly reduced, and due to the increased nucleation
energy barrier, the Mg2 Sn phase is easy to nucleate at one end of the rod to form a “T”
shaped phase, resulting in the a shorter length than that of ordinary β1 ’ [31,32], which
is consistent with the result in Figure 6b. Figure 7c is the HRTEM of β1 ’ in the single-
aged treatment of ZTM641-1Al alloy. According to the FFT of β1 ’ in Figure 7d, it can be
−−
verified that the orientation relationship between β1 ’ and matrix is: [2 1 10]α-Mg //[0001]β1’ ,
−
(0002)α-Mg //( 2110)β1’ [33,34].

3.2. Mechanical Properties

3.2.1. Mechanical Properties at Room Temperature
Figure 8 shows the mechanical properties of the as-aged ZTM641-xAl alloys at room
temperature. The performances of double-aged alloys are better than those of the single-
aged alloys. However, considering the time cost, single-aged treatment is appropriate for
this series of alloys. In general, regardless of single-aged alloys or double-aged alloys,
when Al element increases, the strength of as-aged alloys gradually decreases, and the
elongation first increases while a further quantity decreases. Nie et al. [35], showed that
phases and interface are important factors affecting the properties of alloys. Therefore, the
properties are discussed from these two aspects. First, when the content of Al is 0.2%, no
new phase is generated, and Al element is mainly dissolved in the matrix. On the one
hand, according to the literature [36], Al element can effectively reduce the layer fault
energy of the alloy, on the other hand, a part of Al element is gathered at the grain
boundary, which can promote grain boundary slip and improve the plasticity of the
alloy. However, Al atomic segregation is not conducive to the enhancement of strength.
When the content of Al increases to 0.5%, the Al8 Mn5 phase is gradually formed. At
this time, the size of phases is small, and the distribution is more dispersed, in which
the small precipitated phases dispersed within the grain can play the role of pinning
dislocation, slowing down the rate of dislocation accumulation at the grain boundary
during material deformation, and improving the storage capacity of dislocation within
the material. When the alloy is deformed, it may start more slip systems and improve
the elongation. Moreover, according to the previous microstructure analysis (Figure 4),
the grain size of ZTM641-0.5Al alloy is the smallest. When the grain size is smaller, the
smaller force shared by each grain, the easier movement between them, and the more
conducive they are to plastic de-formation. This is the reason why the ZTM641-0.5Al
alloy has the best elongation. When the content of Al increases to 1%, the Mg32 (Al,Zn)49
phase and Al11 Mn5 phase appear in the alloy, and the number of precipitated phases
increases. When Al element continues to rise to 3%, the Al2 Mg5 Zn2 phase appears. It
is worth noting that the Al11 Mn5 phase, Mg32 (Al,Zn)49 and Al2 Mg5 Zn2 phases are all
brittle phases, the large brittle phases can easily to become a crack source during the tensile
process, so their appearance will deteriorate the properties of alloys. Furthermore, when Al
content increases, the increasingly precipitated phases are distributed on the matrix and
grain boundaries, resulting in the cleavage of the matrix, which reduces the coordinated
deformation ability, then, the plasticity of alloys significantly deteriorates. Combined
with strength and plasticity, the double-aged ZTM641-0.2Al exhibits favorable mechanical
properties at room temperature, the UTS, YS and elongation are 384 MPa, 360 MPa and
9%, respectively.
Figure 9 shows the secondary electron (SE) and BSE-SEM microscope observations of
single-aged ZTM641, ZTM641-0.5Al and ZTM641-2Al alloys at room temperature. From
Figure 9a,d,g, we can find cleavage planes, dimples, tear edges and granular bumps in
fracture surface, and these characteristics are suggestive of mixed fracture. For ZTM641
alloy, many cleavage planes are generated in coarse grains, as shown in Figure 9a, which
Materials 2023, 16, 109 9 of 16

is consistent with Figure 2b. The quantity and size of the cleavage planes decreases with
a small quantity of Al element. However, the fracture mode of ZTM641-2Al alloy is not
changed significantly. From BSE-SEM images, combined with the EDS results, the phase of
the white color is Mg2 Sn, white and gray is a mixed compound of MgZn2 and Mg2 Sn, and
gray bulk phase is Al11 Mn4 , which is consistent with above results and previous reports [37].
For ZTM641-2Al alloy, the number of phases slightly increases, and cracks appear in some
coarse phases. The mixed phases greatly reduce the bonding force between the matrix, and
cracks are easily formed during deformation process. Moreover, according to previous
research [17,20,38], on the one hand, the α-Mn phase can become nucleation cores of
strengthening β1 ’ phase in as-aged treatment process, but when Al content increases, Mn
combines with Al element to form Al-Mn phases. On the other hand, the purification effect
of Mn decreases with a high amount of the Al element, which increases the possibility of
Materials 2022, 15, x FOR PEER REVIEW 10 of 17
alloy defects. Consequently, the beneficial effects of Al content are covered by the above
adverse effects for high Al-containing alloys, which leads to worse mechanical properties.

Figure 8. Mechanical properties of the as-aged ZTM641-xAl alloys at room temperature, (a) single
Figure 8. Mechanical properties of the as-aged ZTM641-xAl alloys at room temperature, (a) single
age, (b) double age.
age, (b) double age.

Figure 9 shows the secondary electron (SE) and BSE-SEM microscope observations
of single-aged ZTM641, ZTM641-0.5Al and ZTM641-2Al alloys at room temperature.
From Figure 9a,d,g, we can find cleavage planes, dimples, tear edges and granular bumps
in fracture surface, and these characteristics are suggestive of mixed fracture. For ZTM641
alloy, many cleavage planes are generated in coarse grains, as shown in Figure 9a, which
 Materials 2022, 15, x FOR PEER REVIEW 11 of 17

purification effect of Mn decreases with a high amount of the Al element, which increases
Materials 2023, 16, 109
the possibility of alloy defects. Consequently, the beneficial effects of Al content are cov-
10 of 16
ered by the above adverse effects for high Al-containing alloys, which leads to worse me-
chanical properties.

Figure9.9. (a,d,g)
Figure (a,d,g) SE-SEM,
SE-SEM, (b,e,h)
(b,e,h) BSE-SEM
BSE-SEM micrographs
micrographs of
of fracture
fracture surface
surface ofofthethesingle-aged
single-aged
ZTM641-xAl alloys tested at room temperature, (a,b) x = 0, (d,e) x = 0.5, (g,h) x = 2, (c,f,i) correspond-
ZTM641-xAl alloys tested at room temperature, (a,b) x = 0, (d,e) x = 0.5, (g,h) x = 2, (c,f,i) corre-
ing EDS results of the points indicated in (b,e,h).
sponding EDS results of the points indicated in (b,e,h).

Figure1010shows
Figure showsthe theimages
images of of single-aged
single-aged ZTM641-xAl
ZTM641-xAl alloys
alloys tested
tested at room
at room tem-
temper-
perature.
ature. For ZTM641
For ZTM641 alloy,alloy,
a largea large
number number
of twinsof are
twins are found.
found. When Al When Al content
content in-
increases,
creases, the twin density first increases and then decreases. The grain size
the twin density first increases and then decreases. The grain size exhibits opposite phe- exhibits oppo-
site phenomenon:
nomenon: the number
the number of phases of phases
gradually gradually increases,
increases, which which is consistent
is consistent with Fig-
with Figure 2.
ure 2. Since twins have the effect of coordinating deformation, the
Since twins have the effect of coordinating deformation, the decrease in the numberdecrease in the number
of
of twins
twins indicates
indicates thatthat
thethe alloy
alloy exhibits
exhibits worse
worse elongation.Furthermore,
elongation. Furthermore,for forZTM641-2Al
ZTM641-2Al
alloy,we
alloy, wecan
canclearly
clearlysee
seethat
thatthe
thebulk
bulkphases
phasesarearemainly
mainlydistributed
distributedon ongrain
grain boundary,
boundary,
andcracks
and cracksmainly
mainlyoccur
occurhere,
here,which
whichindicates
indicatesthat
thatthe
thecrack
crackmay
mayfirst
firstoccur
occurfrom
fromthe
thestress
stress
concentration caused by bulk phases, resulting in the fracture of the alloy. According toto
concentration caused by bulk phases, resulting in the fracture of the alloy. According
theEDS
the EDSline
lineprofile
profileresult
resultfrom
fromFigure
Figure10e,10e,the
thebulk
bulkphases
phasesmainly
mainlycontain
containAl Aland
andMn Mn
elements, combined with Figure 9i, which can be determined as
elements, combined with Figure 9i, which can be determined as the Al-Mn phase. This the Al-Mn phase. This
indicatesthat
indicates thatexcessive
excessiveAl-Mn
Al-Mnphases
phaseshave
haveaapoor
pooreffect
effecton
onproperties.
properties.

3.2.2. Mechanical Properties at Elevated Temperature

Figure 11 shows the mechanical properties of double-aged ZTM641-xAl (x = 0, 0.2, 0.5,
1, 2, 3 and 4%) alloys at 150 ◦ C and 200 ◦ C. We can see from Figure that the mechanical
properties are obviously affected by temperature. It is obvious that the properties of alloys
at 150 ◦ C are generally better than those at 200 ◦ C. Further, when the tensile tests are
carried out at 150 ◦ C, from Figure 11a, we can find that the elongation is improved by a
small amount of Al. The ZTM641-0.2Al alloy has the highest elongation. According to the
analysis in Figure 8, we know that when 0.2%Al is added to the alloy, Al element can reduce
the layer fault energy of the alloy and improve the plasticity. When the deformation tem-
perature increases (150, 200 ◦ C), the amplitude of thermal vibration of all atoms—including
Al—increases, the Critical Resolved Shear Stress of non-base slip decreases, and a variety
of slip systems start to participate in the coordinated deformation, which greatly improves
the high-temperature plasticity of the alloy. When Al element is added to 0.5%, it can be
seen from the previous analysis that its combination with Mn element generates Al8 Mn5
phase with a small particle size. The fine, precipitated phase dispersed in grains can play
the role of pinning dislocation and slow the accumulation rate of dislocation at the grain
 Materials 2023, 16, 109 11 of 16

boundary during material deformation. However, when the deformation is performed at a

higher temperature (150, 200 ◦ C), the activation energy of atoms decreases, the activity of
atoms is higher, and the hindrance effect of the tiny precipitated phase is reduced, which
causes the dislocations stored in the original materials to relax, further, deformation at
this temperature is not conducive to the operation of a greater number of slip systems,
and the properties of the alloy are reduced. When Al element increases further, as can be
seen from Figure 1, the Mg32 (Al,Zn)49 phase, Al11 Mn5 phase and Al2 Mg5 Zn2 phase appear
successively. As mentioned above, the Al-Mn phase, Mg32 (Al,Zn)49 phase and Al2 Mg5 Zn2
phase are all brittle phases. Due to the high content of Al, the particle size of precipitated
phase is large, which is not conducive to coordinated deformation, but can also easily
become a crack source and reduce the plasticity of the alloy. It is worth noting that these
phases are also thermally stable phases. Among them, the melting points of Mg32 (Al,Zn)49
phase and Al11 Mn5 phase are 535 ◦ C and 393 ◦ C, respectively. When the alloy is stressed
and deformed at a high temperature, due to the high melting point, these precipitated
phases are not easy to soften, which can nail grain boundaries, hinder dislocation slip and
improve the strengths. The nailing effect satisfies the Zener formula [39]:

3fγ
FZ = (1)
2r
where f is the volume fraction of the phase, γ is the grain boundary energy and r is the
average size of the phase. As can be seen from the formula, the size of phase is smaller
and the number is larger, and the nailing effect is more obvious. Among these alloys
(ZTM641-xAl, x = 1, 2, 3, 4), the size of the precipitated phases of ZTM641-1Al is relatively
small, so the strengthening effect is the best. In addition, the decreasing trend of strength
is smoother than that of room temperature. The reason for this may be the mutual effect
of the decreasing difference between strong plane and secondary dense row, as well as
the decreasing volume fraction of bulk phases compared with room temperature, which
is further explained in Figure 12 [40]. The alloy with the best combination of strength
and elongation is ZTM641-0.2Al alloy, the UTS, YS and elongation are 212 MPa, 196 MPa
and 29%, respectively. Compared with ZTM641 alloy, the strength of this alloy is slightly
worse, but the elongation is relatively higher. When the tensile tests are carried out at
200 ◦ C, the strength variation tendency of mechanical properties is similar to that at 150 ◦ C.
Materials 2022, 15, x FOR PEER REVIEW 12 of 17
The ZTM641-0.2Al alloy exhibits comprehensive mechanical properties, the UTS, YS and
elongation are 150 MPa, 139 MPa and 23%, respectively.

Figure10.10.Optical
Figure Opticalimages
images (a–c) andand
(a–c) SE-SEM (d) from
SE-SEM longitudinal
(d) from sections
longitudinal of the single-aged
sections of the single-aged
ZTM641-xAl
ZTM641-xAl alloys
alloys adjacent
adjacent fracture
fracture surface
surface tested
tested at room
at room temperature,
temperature, (a) x =(a) x = x0,=(b)
0, (b) 0.5,x(c,d)
= 0.5, (c,d) x
x==22alloy
alloy and (e)EDS
and (e) EDSline
lineprofile
profile in in (d).
(d).

3.2.2. Mechanical Properties at Elevated Temperature

Figure 11 shows the mechanical properties of double-aged ZTM641-xAl (x = 0, 0.2,
0.5, 1, 2, 3 and 4%) alloys at 150 °C and 200 °C. We can see from Figure that the mechanical
properties are obviously affected by temperature. It is obvious that the properties of alloys
 is further explained in Figure 12 [40]. The alloy with the best combination of strength and
elongation is ZTM641-0.2Al alloy, the UTS, YS and elongation are 212 MPa, 196 MPa and
29%, respectively. Compared with ZTM641 alloy, the strength of this alloy is slightly
worse, but the elongation is relatively higher. When the tensile tests are carried out at 200
°C, the strength variation tendency of mechanical properties is similar to that at 150 °C.
Materials 2023, 16, 109 12 of 16
The ZTM641-0.2Al alloy exhibits comprehensive mechanical properties, the UTS, YS and
elongation are 150 MPa, 139 MPa and 23%, respectively.

Figure 11.
Figure 11. Mechanical
Mechanical properties
properties of
of the
the double-aged
double-agedZTM641-xAl
ZTM641-xAlalloys
alloystested
testedatatdifferent
differenttempera-
temper-
atures, (a) ◦
150 °C and (b) ◦
200
tures, (a) 150 C and (b) 200 C. °C.

Figure 12 shows the SE and BSE-SEM microscope observations for double-aged

ZTM641, ZTM641-0.2Al and ZTM641-2Al alloys at 200 ◦ C. For ZTM641 alloy, the frac-
ture of the alloy is featured by cleavage plane, microporous, tear edges and granular
bumps, which are the characteristics of mixed fracture. For ZTM641-0.2Al, the cleavage
plane can hardly be seen, and it is confirmed as ductile fracture. Through the BSE image and
EDS data in Figure 12d, the white and gray colors are mainly a mixed compound of MgZn2
and Mg2 Sn. When Al element reaches 2%, as shown in Figure 12e, the fracture morphology
is similar to that of Figure 12a, indicating that the fracture mode of ZTM641-2Al alloy is also
mixed fracture. By observing Figure 12f, combined with energy spectrum line scanning, it
is found that the dotted gray phase is mainly Al and Mn elements, and it can be concluded
that this is the Al-Mn phase.
Figure 13 shows the optical images and BSE-SEM of double-aged ZTM641-0.2Al and
ZTM641-2Al alloys at 150 ◦ C and 200 ◦ C. For 150 ◦ C, a lot of discontinuity precipitates in
ZTM641-0.2Al alloy are distributed along grain boundaries and in grains. In comparison,
the ZTM641-2Al alloy contains larger sized and a greater number of precipitates distributed
along the grain boundaries. This indicates that stress concentration and crack are likely
to occur along the grain boundaries, resulting in worse elongation, which is consistent
with mechanical properties. At 200 ◦ C, the number of precipitates within grains is sig-
 Materials 2023, 16, 109 13 of 16

nificantly reduced, and the precipitates along the grain boundaries become continuous.
Combined with above analysis in Figures 5 and 12f, the bulk phases are Al-Mn. In a word,
for ZTM641-2Al alloy, the continuous distribution of the precipitates at grain boundary
and increasing temperature leads to the weakening of inter-grain bonding force, leading to
worse elongation with increasing temperature, as is consistent with the properties. More-
over, although twins are found in the ZTM641-2Al alloy, the above-mentioned adverse
effects on elongation are not eliminated. On the contrary, for ZTM641-0.2Al alloy, with
the increasing temperature, the size of the precipitates become finer, and the twins are
Materials 2022, 15, x FOR PEER REVIEW 14 of 1
beneficial to the coordinated deformation, which leads to a certain degree of improvement
in the elongation.

Figure
Figure 12.12. (a,c,e)
(a,c,e) SE-SEM,
SE-SEM, (b,d,f)
(b,d,f) and BSE-SEM
and BSE-SEM micrographs
micrographs of the fracture
of the fracture surface ofsurface of double-age
double-aged
ZTM641-xAl alloys tested at ◦200 °C, (a,b) x = 0, (c,d) x = 0.2 and (e,f)
ZTM641-xAl alloys tested at 200 C, (a,b) x = 0, (c,d) x = 0.2 and (e,f) x = 2. x = 2.

Figure 12 shows the SE and BSE-SEM microscope observations for double-age

ZTM641, ZTM641-0.2Al and ZTM641-2Al alloys at 200 °C. For ZTM641 alloy, the fractur
of the alloy is featured by cleavage plane, microporous, tear edges and granular bump
which are the characteristics of mixed fracture. For ZTM641-0.2Al, the cleavage plane ca
hardly be seen, and it is confirmed as ductile fracture. Through the BSE image and ED
data in Figure 12d, the white and gray colors are mainly a mixed compound of MgZn
and Mg2Sn. When Al element reaches 2%, as shown in Figure 12e, the fracture morpho
ogy is similar to that of Figure 12a, indicating that the fracture mode of ZTM641-2Al allo
is also mixed fracture. By observing Figure 12f, combined with energy spectrum line scan
 to worse elongation with increasing temperature, as is consistent with the properties
Moreover, although twins are found in the ZTM641-2Al alloy, the above-mentioned ad
verse effects on elongation are not eliminated. On the contrary, for ZTM641-0.2Al alloy
with the increasing temperature, the size of the precipitates become finer, and the twin
Materials 2023, 16, 109 14 of 16
are beneficial to the coordinated deformation, which leads to a certain degree of improve
ment in the elongation.

Figure13.13.Optical
Figure Opticalimages
images(a–d) and and
(a–d) BSE-SEM
BSE-SEM(e) from
(e) longitudinal sectionssections
from longitudinal adjacent adjacent
to fractureto fractur
◦ C (a,c) and 200 ◦ C (b,d,e) of the double-aged ZTM641-xAl alloys, (a,b) x = 0.2,
surfacetested
surface tested at 150
at 150 °C (a,c) and 200 °C (b,d,e) of the double-aged ZTM641-xAl alloys, (a,b) x = 0.2
(c–e)x x= =2,2,
(c–e) (f)(f) corresponding
corresponding EDSEDS result
result of theofpoint
the point indicated
indicated in (e). in (e).

4. Conclusions
4. Conclusions
The effects of Al addition (0, 0.2, 0.5, 1, 2, 3 and 4%) on the microstructure and
The effects
mechanical of Al
properties of addition (0, 0.2, 0.5,
the aged ZTM641 alloy1,were
2, 3 systematically
and 4%) on the microstructure
investigated in this and me
chanical
paper. Theproperties
conclusionsof
canthe
beaged ZTM641asalloy
summarized were systematically investigated in this pa
follows:
1.per.There
The conclusions
is a differencecan be summarized
between as follows:
the single-aged and double-aged microstructure. The
aged ZTM641 alloy mainly consists of α-Mg,
1. There is a difference between the single-aged and α-Mn, MgZn 2 and Mg2 Sn microstructure.
double-aged phases. The Th
Al element mainly forms
aged ZTM641 alloy mainly Al 8 Mn , Al
consists
5 Mn , Al
11 of4 α-Mg,
2 Mg Zn
α-Mn,
5 2 and Mg (Al,Zn)
MgZn322 and Mg49 2phases.
Sn phases. Th
With increases
Al element in the forms
mainly addition
Alof Al, the average grain size first decreases and then
8Mn5, Al11Mn4, Al2Mg5Zn2 and Mg32(Al,Zn)49 phases. Wit
increases, and the undissolved phases increase. The average grain size of ZTM641-
increases in the addition of Al, the average grain size first decreases and then in
0.5Al alloy is the smallest, and the single-aged and double-aged grain sizes are 14 µm
creases,
and 12 µm,and the undissolved phases increase. The average grain size of ZTM641
respectively.
2. The mechanical properties of double-aged alloys are superior to single-aged alloys.
The Al element can improve the comprehensive properties at room temperature,
150 ◦ C and 200 ◦ C. The double-aged ZTM641-0.2Al alloy exhibits favorable mechani-
cal properties at room temperature, the UTS, YS and elongation are 384 MPa, 360 MPa
and 9%, respectively. Furthermore, the double-aged ZTM641-0.2Al alloy exhibits
Materials 2023, 16, 109 15 of 16

comprehensive mechanical properties at 150 ◦ C, that is, the UTS, YS and elongation
are 212 MPa, 196 MPa and 29%, respectively, which is about 45% higher than that of
elongation of ZTM641.
3. At room temperature, the ZTM641-xAl alloys exhibit mixed fracture. At 200 ◦ C,
with increases in the Al content, the fracture mechanisms of alloys are mixed frac-
ture, ductile fracture and mixed fracture, respectively. Furthermore, the elongation
of ZTM641-xAl (x ≤ 0.5%) decreases when the temperature rises from 150 ◦ C to
200 ◦ C, which is mainly due to coarse phases at the grain boundaries that can easily
cause microcracks.

Author Contributions: Conceptualization, C.H. and Z.Y.; methodology, L.L. and N.Z.; formal analy-
sis, C.H.; investigation, Z.Y.; resources, X.O.; data curation, F.Q.; writing—original draft preparation,
C.H.; writing—review and editing, F.Q. and L.W.; visualization, J.C.; supervision, J.S.; project admin-
istration, F.Q.; funding acquisition, F.Q. All authors have read and agreed to the published version of
the manuscript.
Funding: This work was supported by National Natural Science Foundation of China (52271117),
Hunan Provincial Natural Science Foundation of China (2021JJ30646), Educational Commission of
Hunan Province of China (20B579), High Technology Research and Development Program of Hunan
Province of China (2022GK4038).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All data are available from the corresponding author upon reasonable
request.
Conflicts of Interest: The authors declare no conflict of interest.

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