Journal of Alloys and Compounds 530 (2012) 71–80

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Journal of Alloys and Compounds

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Effects of Sc and Zr microalloying additions on the microstructure and

mechanical properties of new Al–Zn–Mg alloys
Ying Deng a,∗ , Zhimin Yin a , Kai Zhao a , Jiaqi Duan a , Zhenbo He b
a
School of Materials Science and Engineering, Central South University, Hunan, Changsha 410083, China
b
Northeast Light Alloy Co. Ltd., Hei Longjiang, Harbin 150060, China

a r t i c l e i n f o a b s t r a c t

Article history: Effects of Sc and Zr microalloying additions on the microstructure and mechanical properties of new
Received 23 December 2011 Al–Zn–Mg alloys alloyed with a small amount of copper were investigated comparatively by tensile
Received in revised form 26 March 2012 tests and microscopy methods. Compared with the strength of peak-aged Al–Zn–Mg alloy, the yield
Accepted 26 March 2012
strength increased by 66 MPa after adding 0.10 wt.% Sc and 0.10 wt.% Zr, and improved by 96 MPa after
Available online 5 April 2012
adding 0.25 wt.% Sc and 0.10 wt.% Zr, respectively. Introduction of 0.10 wt.% Zr to Al–Zn–Mg alloy, the
grain refinement effect of scandium did not occur by adding only 0.10 wt.% Sc, but appeared with an
Keywords:
increase in scandium content to 0.25 wt.%. In the presence of 0.10 wt.% Zr, antirecrystallized effect of
Aluminum alloys
Precipitation
scandium appeared at 0.10 wt.% scandium concentration, and enhanced with an increase in the content
Mechanical properties of scandium. Main aging precipitates were two kinds of GP zones in under-aged alloys, and ␩ phases in
Microstructure peak-aged alloys, respectively. Small additions of Sc and Zr did not retard or suppress the formation of
Electron microscopy aging precipitates in Al–Zn–Mg–Sc–Zr alloys. The strengthening effect from aging precipitates was much
stronger than from Sc and Zr microalloying additions in Al–Zn–Mg–Sc–Zr alloys. In addition, the most
important strengthening mechanisms of Sc and Zr microalloying in aged Al–Zn–Mg alloys was Orowan
strengthening of secondary Al3 (Sc, Zr) particles.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction that was attributed to precipitation of Zr-enriched outer shells onto

Of all microalloying additions to Al, Sc and Zr offer the great-
est potential for developing new lightweight structural materials
with excellent mechanical properties, good welding performance
and desirable corrosion and creep resistance [1–6]. Mukhopad-
hyay [7] found that in Al–Zn–Mg–Cu alloy containing both Zr
and Sc as the dispersoid forming elements, the recrystallized
grains were very stable against coarsening, and the total elon-
gation value can reach 916%, exhibiting high superplasticity.
Dev [8] observed that addition of scandium led to very signifi-
cant grain refinement in the fusion zone especially for scandium
levels greater than the eutectic composition (0.55 wt.%). Desir-
able service performance from additions of minor Sc and Zr in
aluminum alloys is mainly attributed to the presence of coher-
ent, L12 -ordered Al3 (Sc, Zr) particles [4,9,10]. The reports about
the aluminum alloys with scandium and zirconium additive
s are available but mainly concentrated on the precipitation behav-
iors of Al3 (Zr, Sc) particles [11,12]. Knipling [13] observed that,
above 325 ◦ C, Zr additions provided a secondary strength increase
∗ Corresponding author. Tel.: +86 731 88830262; fax: +86 731 88830262.
E-mail address: csudengying@163.com (Y. Deng).
the Al3 Sc precipitates, leading to a peak microhardness of 618 MPa
at 400 ◦ C for Al–0.06Sc–0.06Zr. Van Dalen [14] and Booth-Morrison
[15] indicated that additions of Zr and Sc improved coarsening
resistance of Al3 (Sc, Zr) (L12 ) precipitates compared with Al3 Sc
(L12 ).
High-strength thermally strengthened weldable alloys based on
the Al–Zn–Mg system are used extensively for structural applica-
tions in aerospace industry [16–19], and recently reported to be
alloyed with a small amount of copper, which improves consider-
ably the resistance of the base metal and especially that of welded
joints to corrosion cracking and slow disruption. Though the pres-
ence of copper intensifies the formation of hot cracks in welding of
aluminum alloys, this drawback is eliminated by the introduction
of a combined scandium and zirconium additive [20].
However, the systematical and comparative study on the
synergistic effect of Sc and Zr microalloying additions on the
microstructure and properties of new Al–Zn–Mg alloys alloyed
with a small amount of copper is not available. The purpose of this
work is to study the relationship between the mechanical behavior
and microstructure characteristics of new Al–Zn–Mg alloys with
different scandium and zirconium additives, to understand the
microalloying mechanisms of Sc and Zr additions in new Al–Zn–Mg
alloys.

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http://dx.doi.org/10.1016/j.jallcom.2012.03.108
72 Y. Deng et al. / Journal of Alloys and Compounds 530 (2012) 71–80
Table 1
Chemical composition of studied alloys (in wt.%).
Alloy Zn Mg Sc Zr
Al–Zn–Mg 5.39 1.91 – –
Al–Zn–Mg–0.10Sc–0.10Zr 5.36 1.90 0.10 0.10
Al–Zn–Mg–0.25Sc–0.10Zr 5.41 1.98 0.25 0.10
2. Experimental procedures
Three kinds of Al–Zn–Mg alloys with and without Sc and Zr additions were
applied for comparative research. Semi-continuous ingots, with 172 mm in diam-
eter, were provided by Northeast Light Alloy Co. Ltd. Table 1 shows their chemical
compositions. After homogenization treatment (350 ◦ C × 8 h + 470 ◦ C × 12 h: the
purpose of the pretreatment at 350 ◦ C for 8 h is to promote the nucleation of fine
and disperse Al3 (Zr, Sc) particles [12,13,21]; the aim of the final treatment at 470 ◦ C
for 12 h is to eliminate non-equilibrium eutectic phases), the ingots with dimension
of Ø172 mm × 70 mm, were inter-annealed at 420 ◦ C for 4 h, then hot rolled to 7 mm
thick plates immediately. Then the hot rolled plates were annealed at 420 ◦ C for 1 h,
and cold rolled to 2 mm sheets. The sheets were subjected to solution treatment
at 470 ◦ C for 1 h, followed by water quenching, and then aged at 120 ◦ C for 24 h.
The selection of heat treatment parameters was based on the results reported in
reference [2].
In order to investigate the effects of scandium and zirconium microalloying addi-
tions in Al–Zn–Mg alloys, the microstructure and properties of Al–Zn–Mg alloys with
different Sc and Zr contents were studied comparatively by hardness measurements,
tensile tests, scanning electron microscopy (SEM), energy dispersive spectroscopy
(EDS), transmission electron microscopy (TEM), electron back scattered diffraction
(EBSD) technique and high resolution electron microscopy (HREM) methods. Hard-
ness measurements were finished on an HW187.5 Brinell’s machine. The mechanical
testing utilized transverse orientation (normal to rolling direction) specimens. Ten-
sile properties were performed on a CSS-44100 electronic universal testing machine
with 2 mm/min loading speed. Yield strength of materials was identified at 0.2%
plastic strain. A minimum of six hardness measurements and mechanical tests was
performed on each sample, and their statistical scatter determined the measure-
ment errors. All of the experimental errors reported here represented one standard
deviation from the mean. SEM observations were carried out on a Quanta MK2-200
SEM, operating at 20 kV. Thin foils for transmission electron microscope (TEM) and
high resolution electron microscope (HRTEM) observations were sectioned from
the alloys under different conditions. The foils were prepared by twin-jet electro-
polishing at 20 V in a solution of 30% nitric acid and 70% methanol solution cooled
to −30 ◦ C and observed on a TECNAIG2 20 electron microscope and a JEM-3010
electron microscope respectively, both with an acceleration voltage of 200 kV. EBSD
analyses were performed using a Sirion 200 field emission gun scanning electron
microscope equipped with EBSD system. EBSD data were subsequently analyzed by
the OIM Analysis 5 software. The orientation uncertainty or “orientation noise” in
deformed samples (aged alloy) was greater than in homogenized samples. Therefore
in order to avoid spurious boundaries, misorientations below 2◦ were not measured.
This limit was used for all samples in order to provide consistent quantitative data.
Boundaries with misorientations between 2◦ and 15◦ were defined as low angle grain
boundaries (LAGB) and those of misorientation >15◦ as high angle grain boundaries
(HAGB).
3. Results
3.1. Effect of Sc and Zr microalloying additions on tensile
properties
Table 2 shows tensile properties of the Al–Zn–Mg alloys with
different Sc and Zr additions under different conditions. Com-
pared with the mechanical properties of peak-aged Al–Zn–Mg
alloy, the yield strength and the ultimate tensile strength increased
by 66 MPa and 31 MPa after adding 0.10 wt.% Sc and 0.10 wt.%
Table 2
Mechanical properties of Al–Zn–Mg alloys with different Sc and Zr additives under different processing conditions.
Alloys Condition YS (MPa)
Al–Zn–Mg Solution treated 183 ± 3
Peak aged 439 ± 2
Al–Zn–Mg–0.1Sc–0.1Zr Solution treated 252 ± 2
Peak aged 505 ± 3
Al–Zn–Mg–0.25Sc–0.1Zr Solution treated 275 ± 1
Peak aged 535 ± 5
Cu Mn Si Fe Al
0.34 0.33 0.08 0.16 Bal.
0.25 0.32 0.09 0.19 Bal.
0.33 0.32 0.11 0.18 Bal.
Zr, respectively, and improved by 96 MPa and 58 MPa by adding
0.25 wt.% Sc and 0.10 wt.% Zr, respectively, meanwhile the elon-
gations all kept above 12% in two peak-aged Al–Zn–Mg–Sc–Zr
alloys. The strength increments can be explained by strength-
ening due to additions of Sc and Zr. Moreover, with the
increase of scandium additions, the strength increased and the
elongation decreased. The yield strength increment caused by
aging treatment was up to 256 MPa, 253 MPa and 260 MPa in
Al–Zn–Mg alloy, Al–Zn–Mg–0.10 wt.% Sc–0.10 wt.% Zr alloy and
Al–Zn–Mg–0.25 wt.% Sc–0.10 wt.% Zr, respectively. The substantial
increase in the yield strength after aging was evidently related to
age strengthening. Besides, obviously, strengthening effect from
aging precipitates (253 MPa and 260 MPa) was much larger than
from microalloying additions of Sc and Zr (66 MPa and 96 MPa) in
Al–Zn–Mg alloy.
3.2. Effect of Sc and Zr microalloying additions on grain
microstructures
Fig. 1 is the orientation map with boundaries for homoge-
nized and aged alloys. The fractions of grain boundaries with
different misorientation angles are shown in Fig. 2. The orienta-
tion maps of three homogenized alloys consisted of the grains
with average size of 78.3 ␮m, 79.6 ␮m and 58.4 ␮m in Al–Zn–Mg
alloy, Al–Zn–Mg–0.10Sc–0.10Zr alloy, Al–Zn–Mg–0.25Sc–0.10Zr
alloy respectively. This indicated that making additions of 0.25 wt.%
Sc and 0.10 wt.% Zr to Al–Zn–Mg alloys can refine the grains
of ingots, while the modifying effect did not occur when
the content of Sc was only 0.10 wt.%. The grain boundaries
were all mostly characterized by HAGB. After solution-aging
treatment, recrystallization occurred in Al–Zn–Mg alloy, where
grain boundaries were mostly characterized by HAGB. However,
Al–Zn–Mg–0.10Sc–0.10Zr and Al–Zn–Mg–0.25Sc–0.10Zr peak-
aged alloys still remained unrecrystallized, fiber-like structures.
The fiber-like structures were made up of sub-grains whose
boundaries were characterized by LAGB. Moreover, an increase in
scandium content promoted an increase in LAGB, exhibiting the
misorientation angles between 2◦ and 15◦ , associated to substruc-
ture (Figs. 1 and 2). The grain sizes were 8.26 ␮m, 1.36 ␮m and
0.93 ␮m in aged Al–Zn–Mg alloy, Al–Zn–Mg–0.10Sc–0.10Zr alloy
and Al–Zn–Mg–0.25Sc–0.10Zr alloy, respectively.
SEM images in Fig. 3 show microstructures of as-cast and
homogenized Al–Zn–Mg and Al–Zn–Mg–0.25Sc–0.10Zr alloys.
Serious segregation existed in the two studied as-cast alloys. EDS
results are shown in Table 3. According to EDS analyses, the white
secondary phases as shown in Fig. 3(a)A and Fig. 3(b)C, were both
enriched in Zn and Mg elements non-equilibrium phases. The grey
UTS (MPa) EI (%)
328 ± 1 25.2 ± 0.1
498 ± 1 16.5 ± 0.7
378 ± 3 23.6 ± 0.4
529 ± 2 14.1 ± 0.6
397 ± 3 23.3 ± 0.3
556 ± 2 12.1 ± 0.4
 Y. Deng et al. / Journal of Alloys and Compounds 530 (2012) 71–80 73

Fig. 1. Orientation maps of specimens under different conditions. Al–Zn–Mg alloy: (a) homogenized and (d) aged; Al–Zn–Mg–0.10Sc–0.10Zr alloy: (b) homogenized and (e)
aged; Al–Zn–Mg–0.25Sc–0.10Zr alloy: (c) homogenized and (f) aged; (g) representation of different color lines used to identify the boundaries with different misorientation
angles in (a)–(f); (h) direction of specimens in (d)–(f). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)

100
Boundary levels (misorientation angle)
phases as shown in Fig. 3(a)B and Fig. 3(b)D were enriched in Fe
LAB 2-15° and Mn elements indissoluble impurity phases. After homogeniza-
HAB 15-180° tion treatment, enriched in Zn and Mg non-equilibrium phases
80 dissolved into matrix, and only small indissoluble impurity phases
remained (Fig. 3(c)F and (d)G). Compared with Al–Zn–Mg alloy, an
additional typical characteristic of Al–Zn–Mg–0.25Sc–0.10Zr alloy
60 was the presence of primary Al3 (Sc, Zr) particles, distributed ran-
Frequency/%

domly in the center of some grains (Fig. 3(b)E and (d)H).

TEM images in Fig. 4 show microstructures of the three
40 aged alloys. Compared with the microstructure of Al–Zn–Mg
alloy consisted of recrystallized grains, the structure of
Al–Zn–Mg–0.10Sc–0.10Zr and Al–Zn–Mg–0.25Sc–0.10Zr aged
20 alloys both consisted of micro-scaled sub-grain structures. More-
over, with an increase in the content of scandium, the size of
sub-grains decreased. The results are in accordance with EBSD
0 results.
Al-Zn-Mg 0.10 wt%Sc 0.25 wt%Sc Al-Zn-Mg 0.10 wt%Sc 0.25 wt%Sc

Homogenized Aged
3.3. Effect of Sc and Zr microalloying additions on age hardening
Fig. 2. Frequency of different misorientation angles in the three alloys under differ-
ent conditions. Fig. 5 shows the effect of aging time on the hardness of the
three alloys. The three alloys all exhibited typical aging hardening

Table 3
Chemical composition of the secondary phases in Fig. 2 (in at.%).

Phase Al Zn Mg Cu Fe Si Mn Sc Zr Ti

A 65.69 13.94 16.72 3.76 0 0 0 0 0 0

B 78.77 1.64 2.01 0.84 8.86 3.96 3.93 0 0 0
C 68.20 13.07 15.65 3.09 0 0 0 0 0 0
D 83.04 1.42 1.92 0.63 7.49 3.61 1.90 0 0 0
E 76.46 1.83 0 0 0 0 0 11.61 8.73 1.38
F 80.72 1.10 1.10 1.05 10.22 3.25 2.56 0 0 0
G 83.14 1.18 1.35 0.73 8.82 3.27 1.51 0 0 0
H 75.52 1.74 0 0 0 0 0 11.85 9.17 1.73
74 Y. Deng et al. / Journal of Alloys and Compounds 530 (2012) 71–80

Fig. 3. SEM microstructures of the two studied alloys under different conditions. Al–Zn–Mg alloy: (a) as-cast and (c) homogenized; Al–Zn–Mg–0.25Sc–0.10Zr alloy: (b)
as-cast and (d) homogenized.

behaviors. Hardness vs. aging time curves in Fig. 5 exhibit three
regions: (1) rapid increase in hardness (under-aging); (2) plateau in
hardness (peak-aging); and (3) decrease in hardness (over-aging).
Three alloys were all in peak-aged T6 state after 24 h of aging at
120 ◦ C. Seen from Fig. 5, the hardness increased by adding Sc and
Zr to Al–Zn–Mg alloys, and the hardness increment was uniform
over the entire ageing process. This indicated that hardening from
minor Sc and Zr was independent of hardening caused by other
aging precipitates in Al–Zn–Mg alloy.
3.4. Effect of Sc and Zr microalloying additions on aging
precipitates in Al–Zn–Mg alloy
TEM images in Fig. 6 show microstructures of the three aged
alloys. A large number of fine precipitates were formed homo-
geneously in grains and along grain boundaries (Fig. 6(a)–(c))
in under aged alloys. With increasing aging time, short rod-like
particles gradually coarsened within grains, and grain boundary
precipitates were formed in peak aged alloys (Fig. 6(d)–(f)). By

Fig. 4. Bright field TEM microstructures of the three aged alloys: (a) Al–Zn–Mg, (b) Al–Zn–Mg–0.10Sc–0.10Zr and (c) Al–Zn–Mg–0.25Sc–0.10Zr.
 Y. Deng et al. / Journal of Alloys and Compounds 530 (2012) 71–80 75

was that the size of grain boundary precipitates and the width of
180 the precipitate free zone were smaller in Al–Zn–Mg–Sc–Zr alloys
(Fig. 6(g)–(i)).

160
3.5. Precipitates in Al–Zn–Mg–Sc–Zr alloys
Al-Zn- Mg
Hardness / HB

140 Al-Zn- Mg-0. 10Sc- 0.10Zr

TEM images in Fig. 7 show precipitates in Al–Zn–Mg–Sc–Zr
Al-Zn- Mg-0. 25Sc- 0.10Zr alloys under different conditions. With semi-continuous casting
and subsequent cooling of ingots, a considerable part of scan-
120 dium and zirconium was fixed in supersaturated solid solution.
During subsequent homogenization treatment, scandium and zir-
conium precipitated from supersaturated ␣(Al) matrix in the form
100 of secondary Al3 (Sc, Zr) particles [9,22–26]. The average size of
Al3 (Sc, Zr) precipitates was estimated from direct measurements
on TEM negatives, and was determined to be about 20 nm in
80
0 10 20 30 40 50 homogenized Al–Zn–Mg–Sc–Zr alloys (Fig. 7(a)–(b)). The presence
Aging time/ h
of Ashby–Brown contrast for bright-field images, as well as the
superstructure reflections like (1, 0, 0) and (1, 1, 0), confirmed
Fig. 5. Age hardening curves. that this particle was Al3 (Sc, Zr) particle with an Ll2 cubic crystal
structure, which was coherent with the Al matrix. The cold rolled
microstructures mainly consisted of dislocation substructures. In
comparison, it was notable that there was almost no difference of addition, many fine spherical particles without Ashby–Brown con-
the size and density of aging precipitates within grains between trast were observed in bright-field images. The [0 1 1] orientation
Al–Zn–Mg alloy and Al–Zn–Mg–Sc–Zr alloy (Fig. 6(a)–(i)). The only diffraction pattern from those particles were performed, show-
difference between the Al–Zn–Mg alloy and Al–Zn–Mg–Sc–Zr alloy ing characteristic super-lattice spots from coherent Al3 (Sc, Zr)

Fig. 6. Bright field microstructural evolution of the three alloys aged at 120 ◦ C. Al–Zn–Mg alloy: (a) under aged, (d) peak aged and (g) over aged; Al–Zn–Mg–0.10Sc–0.10Zr
alloy: (b) under aged, (e) peak aged and (h) over aged; Al–Zn–Mg-0.25Sc–0.10Zr alloy: (c) under aged, (f) peak aged and (i) over aged.
76 Y. Deng et al. / Journal of Alloys and Compounds 530 (2012) 71–80

Fig. 7. Precipitates in Al–Zn–Mg–Sc–Zr alloys under different conditions. Al–Zn–Mg–0.10Sc–0.10Zr alloy: (a) homogenized, (e) aged at 120 ◦ C for 1 h and (i) peak aged;
Al–Zn–Mg–0.25Sc–0.10Zr alloy: (b) homogenized, (c) hot-rolled, (d) solution-treated, (f) aged at 120 ◦ C for 1 h and (j) peak aged; (g and h) HREM images: taken along the
[1 0 0] and [1 1 0] zone axis, aged at 120 ◦ C for 1 h.

precipitates. The loss of Ashby–Brown contrast around secondary
Al3 (Sc, Zr) precipitates in rolled alloys was due to the interfer-
ence of dislocation strain field (Fig. 7(c)). After solution treatment,
unrecrystallized micrometer-sized sub-grains remained. More-
over, Ashby–Brown contrast around Al3 (Sc, Zr) particles for bright
field images appeared again for the release of strain. Al3 (Sc, Zr)
particles strongly pinned sub-grain boundaries (Fig. 7(d)). The
bright field and HREM images of the under-aged alloy are shown
in Fig. 7(e) and (f) and (g) and (h) respectively. In bright field
image under the just Bragg condition, Al3 (Sc, Zr) particles were still
 Y. Deng et al. / Journal of Alloys and Compounds 530 (2012) 71–80
Fig. 7. (Continued ).
coherent with matrix judged from Ashby and Brown contrast which
appeared around a spherical coherent particle in Fig. 7(e) and (f).
The size of coherent Al3 (Sc, Zr) particles kept unchanged during
heat treatment and processing in our research, which was sup-
ported by the work of Iwamura and Miura [27], who reported
that accelerated Al3 (Sc, Zr) particle growth was observed only at
particle diameters larger than 80 nm, while delay in particle coars-
ening was noticed in the particle diameter range of 30–80 nm.
Besides, high resolution images were taken in the Al-projections
1 0 0 and 1 1 0, as shown in Fig. 7 (g) and (h). Contrast fea-
tures in the [1 0 0]Al projection, Fig. 7 (g), were identified as
GP(I)-zones, which appeared as spherical precipitates, 2–8 nm
wide. In the [1 1 0]Al projection, Fig. 7(h), the thin objects were
identified as GP(II)-zones, 3–7 nm wide, which were assumed
to be an early stage in the formation of ␩ -precipitates. The
GP(II)-zones were described as zinc-rich layers on {1 1 1}-planes,
with internal order in the form of elongated 1 1 0 domains
[28]. Therefore, the two types of GP-zones and Al3 (Sc, Zr) parti-
cles were the main strengthening precipitates in the under-aged
Al–Zn–Mg–Sc–Zr alloy. In peak-aged alloy, besides a large number
of coherent secondary Al3 (Sc, Zr) particles, lots of fine precipi-
tates were distributed homogenously in matrix. The SAD pattern
of peak aged alloys in [1 1 2]Al projection was shown in Fig. 7(j).
Besides the spots of Al3 (Sc, Zr) particles, there were some spots
from ␩ phase, which were identified by referring to the model in
some reported results [29]: (10.l) and (20.l) rows in the [1 1 2]Al
77
projection. Therefore, ␩’ phases and Al3 (Sc, Zr) particles were
the main strengthening phases in peak-aged Al–Zn–Mg–Sc–Zr
alloy.
4. Discussion
4.1. The modifying effect attained due to Sc and Zr microalloying
additions to Al–Zn–Mg alloy
In the former Soviet Union, additions of the transition element
scandium (Sc) have been used for a number of years as an alterna-
tive grain refiner to Ti/TiB2 , particularly in the context of welding.
Grain refinement due to the additions of scandium has been pre-
viously shown to arise from the precipitation of primary Al3 Sc
particles in the melt, which act as potent nucleation sites for alu-
minum grains [30]. As the aluminum-rich end of the Al–Sc phase
diagram is dominated by a eutectic reaction between the liquid, ␣-
Al, and Al3 Sc, the grain refinement mechanism only operates with
scandium addition levels greater than the eutectic composition
(0.55 wt.% Sc). Taking into account that the cost of the Al–Sc alloy-
ing combination is high, it is economically inexpedient to introduce
this high content of scandium into industrial alloys (even for air-
craft and spacecraft). Fortunately, the minimum Sc level required
for refinement can be significantly reduced by the addition of Zr
[20,31]. The previous reports [32,33] showed that when Zr addi-
tions were not made, the modifying effect of scandium appears at
78 Y. Deng et al. / Journal of Alloys and Compounds 530 (2012) 71–80
concentrations above 0.55 wt.% (at hypereutectic concentrations),
while in the presence of zirconium (about 0.10 wt.%), the modifying
effect manifests itself at scandium concentration above 0.18 wt.%.
In our research, in the case of 0.10 wt.% Zr additions into Al–Zn–Mg
alloy, the grain refinement effect can be observed when the content
of scandium was 0.25 wt.%, but did not appear at scandium con-
centration of 0.10 wt.% Sc. This result was in good accordance with
the references [32,33]. In fact, an additive consisting of 0.25 wt.%
Sc and 0.10 wt.% Zr replaces the introduction of 0.5–0.6 wt.% Sc
from the standpoint of modifying the cast grain structure of alu-
minum alloys. This saves expensive scandium. The high level of
grain refinement was caused by primary Al3 (Sc, Zr) particles, solid-
ified firstly during solidification, as observed in Fig. 3(b) and (d),
which were active centers for the generation of new grains of solid
solution [34].
4.2. The antirecrystallized effect attained due to making Sc and Zr
microalloying additions to Al–Zn–Mg alloy
As practice of the work with commercial scandium enriched
aluminum alloys shown, optimum scandium content, which
guarantees retention of a nonrecrystallized structure after heat
treatment of semiproducts, depends on an alloy system. Al–Zn–Mg
system based alloys are susceptible to recrystallization to a lesser
extent, and scandium content within a range of 0.15–0.20 wt.%
ensures retention of a non-recrystallized structure of quenched
semiproducts [33]. In our studies, in the presence of 0.10 wt.% Zr, a
nonrecrystallized structure remains at scandium concentration of
0.10 wt.% in Al–Zn–Mg alloy. Therefore, in the presence of 0.10 wt.%
Zr, the scandium content ensuring retention of a non-recrystallized
structure is lower than Zr-free Al–Zn–Mg alloy. Moreover, antire-
crystallized effect of scandium enhances by increasing scandium
additions. High antirecrystallized effectiveness of Sc and Zr addi-
tions is attributed to high density of the fine, coherent, secondary
Al3 (Sc, Zr) dispersoid particles precipitated during decomposition
of solid solution homogeneously, as shown in Fig. 7(a) and (b).
Coherent Al3 (Sc, Zr) particles in the diameter of about 20 nm have a
good thermal stability and drastic antirecrystallized effect. As they
strongly pin dislocation and grain boundaries during heat treat-
ment and processing, a nonrecrystallized structure (substructure)
still remains in aged Al–Zn–Mg–Sc–Zr alloys (Figs. 1, 2 and 4).
4.3. Effects of Sc and Zr microalloying additions on mechanical
properties and aging precipitation
Small additions of Sc and Zr enable a superior combination of
higher strength levels and acceptable ductility in aged alloy. Start-
ing from refining the grain size of cast aluminum alloys, additions
of Sc and Zr also increase the resistance to recrystallization during
hot working and introduce additional strengthening through the
formation of fine coherent secondary Al3 (Sc, Zr) particles. Homo-
geneous distribution of these particles promotes formation of a
stable refined subgrain structure during deformation processing
and heat treatment, which gives an additional increase in strength.
A strength increase due to the secondary Al3 (Sc, Zr) precipitation
can generally occur by one of two mechanisms, depending on
the particle size. These are (i) shearing of small precipitates,
which involves order strengthening, coherency strengthening and
modulus mismatch strengthening; and (ii) the Orowan bypass
mechanism for larger particles, when dislocations cannot move
through but loop around the particles [35]. With an increase in par-
ticle diameter, the YS increases when the first mechanism operates,
while it decreases when the Orowan mechanism operates. Transi-
tion from the shearing mechanism to the Orowan strengthening
mechanism occurs in binary Al–Sc alloys in the particle diameter
range from 4 to 6 nm [22,36,37], suggesting that the Orowan
mechanism should be responsible for the Al3 (Sc, Zr) particle-
induced
strengthening in our studies (20 nm). Therefore, a increase in
the YS after peak aging (66 MPa and 96 MPa) caused by adding
minor Sc and Zr was evidently related to refining strengthening
from primary Al3 (Sc, Zr) particles formed during the solidification
in Al–Zn–Mg–0.25Sc–0.10Zr alloy, substructure strengthening
and Orowan strengthening caused by the secondary Al3 (Sc, Zr)
particles precipitated during homogenization in Al–Zn–Mg–Sc–Zr
alloys. Besides, compared with the mechanical properties reported
in reference [2], the alloy gained 11 MPa yield strength increment
by pretreatment at 350 ◦ C for 8 h during homogenization in aged
Al–Zn–Mg–0.25Sc–0.10Zr alloy.
Wu [26] indicates that the formation of GP(II) zones is sup-
pressed in the presence of zirconium that leads to a reduction in the
amount of ␩ formed during subsequent ageing. However, accord-
ing to the references [28], GP(I)-zones are formed over a wide
temperature range, from room temperature to 140–150 ◦ C, inde-
pendently of quenching temperature. The GP(I)-zones are coherent
with the aluminum matrix, with internal ordering of Zn and Al/Mg
on the matrix lattice, suggested to be based on AuCu(I)-type sub-
unit, and anti-phase boundaries. GP(II) are formed after quenching
from temperatures above 450 ◦ C, by aging at temperatures above
70 ◦ C. The solution-aging treatment in our studies is solution
treated at 470 ◦ C for 1 h, followed by water quenching and then aged
at 120 ◦ C for 24 h, which satisfies the condition of forming two kinds
of GP zones. Moreover, from our observation, two kinds of GP zones
both appear in our studied alloy during the early stage of aging. Fur-
thermore, observed from the microstructures of two aged alloys,
small additions of Sc and Zr do not affect the size and density of
the aging precipitates within grains during aging treatment, except
the grain boundary precipitates and precipitate free zone. There-
fore, we can infer that minor additions of Zr and Sc to Al–Zn–Mg
alloy do not retard or suppress the formation of aging harden-
ing precipitates. This inference is confirmation for the mechanical
property results that the YS increment from aging precipitation is
almost the same among the three studied alloys (256 MPa, 253 MPa
and 260 MPa respectively). Besides, the strengthening effect from
aging precipitates (253 MPa and 260 MPa) is much stronger than
from Sc and Zr microalloying additions (66 MPa and 96 MPa) in
Al–Zn–Mg–Sc–Zr alloys.
4.4. Strengthening mechanisms of Sc and Zr additions
According to the discussion in Sections 4.1–4.3, the strength-
ening mechanisms of Sc and Zr microalloying additions in aged
Al–Zn–Mg alloys can be mainly divided into Orowan strengthening
derived from secondary Al3 (Sc, Zr) particles and gain boundary or
subgrain boundary strengthening. However, the most important
mechanism of Sc and Zr microalloying additions in our stud-
ied alloys is unclear. Therefore, we need to estimate different
strengthening contributions. Due to the limitation of experimental
conditions, we just provided coarse estimation here. We assumed
that the thickness of the TEM-foils in the area of investigation was
about 80 nm, which was the estimation from TEM sample prepa-
ration. The sizes (diameters) and the number density of the Al3 (Sc,
Zr) particles were estimated from TEM images taken at magnifi-
cations of 195 000–380 000. The microstructural features of Al3 (Sc,
Zr) particles in studied aged alloys were shown in Table 4.
4.4.1. Orowan strengthening of Al3 (Sc, Zr) particles
The increase in the YS due to the Orowan strengthening,  Or ,
was given by [22]:
 Gb  d 
Or = K4 M(1 − v)−0.5 ln
s
(1)
 b
 Y. Deng et al. / Journal of Alloys and Compounds 530 (2012) 71–80
Table 4
Microstructural features of Al3 (Sc, Zr) particles in studied aged alloys.
Alloy Al3 (Sc, Zr) particles
dm (nm) N (m−3 )
Al–Zn–Mg–0.10Sc–0.10Zr 20 3 × 1020
Al–Zn–Mg–0.25Sc–0.10Zr 19 5 × 1020
dm
ds =
4 strength increments caused by additions of Sc and Zr were mainly
  0.5  derived from refining strengthening of primary Al3 (Sc, Zr) parti-
1 2 dm
= −1
2 3fV 4 Orowan strengthening caused by the secondary Al3 (Sc, Zr) parti-
where M is the Taylor factor and depends on the texture and the
orientation of the tensile axis, v and G are the matrix Poisson’s ratio
and the shear modulus, respectively, b is the magnitude of the Al
matrix Burgers vector, K4 is a constant, the value which depends on
the particle size and distribution, and ds and  are the mean particle
diameter and an effective inter-particle distance, respectively, both
on the dislocation slip planes. The values in Table 4 and the follow-
ing values of the parameters of Eq. (1) were used to calculate  Or :
K4 = 0.127, M = 3.06, v = 0.331 and G = 27.8 GPa, and b = 0.286 nm, so
that the Orowan strength increments in Al–Zn–Mg–0.10Sc–0.10Zr
and Al–Zn–Mg–0.25Sc–0.10Zr alloys related to the Al3 (Sc, Zr) par-
ticles were about 50 MPa and 65 MPa, respectively.
4.4.2. Grain boundary strengthening (Hall–Petch)
The standard Hall–Petch equation, Eq. (4), was employed to
relate the yield strength of the material () to the average grain
size (d).
H–P = 0 + kd−1/2
In this equation,  0 is the intrinsic resistance of the lattice to
dislocation motion and k is a parameter that describes the rela-
tive strengthening contribution of grain boundaries. A k value of
0.04 MPa × m1/2 [38,39] for aluminum was used to estimate the
strengthening due to grain boundaries.
The increase in the YS due to the grain boundary strengthen-
ing from Sc and Zr microalloying additions,  H–P , was given as
follows:
−1/2 −1/2
H–P = k(dSc-containing − dSc-free )
By substituting of k value and grain sizes in three stud-
ied alloys,  H–P can be calculated, which was about
20 MPa in Al–Zn–Mg–0.10Sc–0.10Zr alloy and 28 MPa in
Al–Zn–Mg–0.25Sc–0.10Zr alloy respectively.
Therefore, the calculated YS increases from Sc and Zr
microalloying additions were about 70 MPa and 93 MPa in
Al–Zn–Mg–0.10Sc–0.10Zr alloy and Al–Zn–Mg–0.25Sc–0.10Zr
alloy, respectively, which approached the experimental results
(66 MPa and 96 MPa). Moreover, it can be seen that, the most impor-
tant mechanism from Sc and Zr additions in Al–Zn–Mg–Sc–Zr alloys
was Orowan strengthening of secondary Al3 (Sc, Zr) particles.
5. Conclusions
Compared with the mechanical properties of peak-aged
Al–Zn–Mg alloy, the yield strength and the ultimate tensile strength
increased by 66 MPa and 31 MPa after adding 0.10 wt.% Sc and
0.10 wt.% Zr, respectively, and improved by 96 MPa and 58 MPa by
adding 0.25 wt.% Sc and 0.10 wt.% Zr, respectively, meanwhile the
elongations all kept above 12% in two peak-aged Al–Zn–Mg–Sc–Zr
alloys. In the case of 0.10 wt.% Zr additives in Al–Zn–Mg alloy, mak-
ing 0.25 wt.% Sc scandium additions refined the grains of ingots,
while the modifying effect did not occur when only 0.10 wt.%
79
Sc was added. In the presence of 0.10 wt.% Zr, antirecrystallized
effect of scandium appeared at 0.10 wt.% Sc concentration, and
enhanced with an increase in the content of scandium. Main aging
precipitates were two kinds of GP zones in under-aged alloys,
fv
and ␩ phases in peak-aged alloys, respectively. Small additions
1 × 10−3
of Sc and Zr did not retard or suppress the formation of aging
1 × 10−3
precipitates in Al–Zn–Mg–Sc–Zr alloy. In addition, the strengthen-
ing effect from aging precipitates was much stronger than from
Sc and Zr microalloying additions in Al–Zn–Mg–Sc–Zr alloys. The
(2)
(3) cles formed during solidification, substructure strengthening and
cles formed during homogenization treatment. Moreover, the most
important strengthening mechanisms of Sc and Zr microalloying
in aged Al–Zn–Mg alloys was Orowan strengthening of secondary
Al3 (Sc, Zr) particles.
Acknowledgments
This work was financially supported by the National Civilian
Matched Project of China (JPPT-115-2-948), the National General
Pre-research Project of China (51312010402), Hunan Provincial
Innovation Foundation for Postgraduate (CX2011B111) and the
Graduate Degree Thesis Innovation Foundation of Central South
University (2011ybjz014).
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