Materials and Design 181 (2019) 107927

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Age-hardening of high pressure die casting AlMg alloys with Zn and

combined Zn and Cu additions
Lukas Stemper a,⁎, Bernhard Mitas b, Thomas Kremmer b, Steffen Otterbach d,
Peter J. Uggowitzer b,c, Stefan Pogatscher a,b,⁎⁎
a
Christian Doppler Laboratory for Advanced Aluminum Alloys, Chair of Nonferrous Metallurgy, Montanuniversitaet Leoben, Franz-Josef Straße 18, 8700 Leoben, Austria
b
Chair of Nonferrous Metallurgy, Montanuniversitaet Leoben, Franz-Josef Straße 18, 8700 Leoben, Austria
c
Laboratory of Metal Physics and Technology, Department of Materials, ETH Zurich, 8093 Zurich, Switzerland
d
Audi AG, N/PG-T52, 74148 Neckarsulm, Germany

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• New high pressure die casting alloys

based on Al-Mg-Zn-(Cu) for structural
cast components are studied.
• Two-step artificial aging can either en-
hance the maximum hardness or accel-
erate the hardening kinetics strongly.
• Heat treatment strategy and alloy
chemistry significantly influence the
microstructural evolution during heat
treatment.

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

Article history: This study investigates the age-hardening of AlMg alloys with Zn and combined Zn and Cu additions. Two
Received 9 April 2019 AlMg5Mn1 alloys modified with Zn and Cu were processed by high pressure die casting (HPDC) and different
Received in revised form 30 April 2019 heat treatment strategies. Single step artificial aging, artificial aging with pre-aging and the effect of the
Accepted 8 June 2019
quenching rate were studied via hardness measurements and transmission electron microscopy (TEM). Single-
Available online 9 June 2019
step artificial aging resulted in an increase in hardness of 58% in peak aged condition for the Zn-only modified
Keywords:
alloy and of 56% for the Zn- and Cu-containing alloy. Pre-aging treatments either reduce the necessary aging
Aluminum alloys time or increase the hardness, depending on the parameters used. Microstructural investigations indicate a sig-
AlMg nificant change in the S- or T-phase precursors, and in precipitation density with pre-aging. The alloys have high
Alloy design potential for use as complex structural HPDC components in lightweight transport applications, but are also of
Hardening behavior general interest for components which require high strength and formability.
Precipitation © 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://
High pressure die casting creativecommons.org/licenses/by-nc-nd/4.0/).

⁎ Corresponding author.
⁎⁎ Correspondence to: S. Pogatscher, Christian Doppler Laboratory for Advanced Aluminum Alloys, Chair of Nonferrous Metallurgy, Montanuniversitaet Leoben, Franz-Josef Straße 18,
8700 Leoben, Austria.
E-mail addresses: lukas.stemper@unileoben.ac.at (L. Stemper), stefan.pogatscher@unileoben.ac.at (S. Pogatscher).

https://doi.org/10.1016/j.matdes.2019.107927
0264-1275/© 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 L. Stemper et al. / Materials and Design 181 (2019) 107927
1. Introduction
One of the most significant changes in people's lives over the last few
decades has involved the growth of transport and traffic. While environ-
mental and sustainable aspects had only minor relevance in earlier
years, they have assumed political and economic importance due to
the rising CO2 emissions associated with increasing traffic [1,2]. A
well-established approach to these challenges in the automotive indus-
try is mass reduction via light-weight construction and materials de-
sign. Besides the substitution of heavy materials such as steel with
light aluminum alloys, a major aspect of light-weighting is the creation
of complex structural components which combine the individual pur-
poses of several parts in one. Although the price of such components
is higher, total costs decrease due to diminished joining effort [3]. Typi-
cal examples can be found in car body applications such as strut hous-
ings or side and cross members. The complex shapes of these,
resulting from varying wall thicknesses and transition radii, makes
them ideal candidates for high pressure die casting (HPDC) in mass pro-
duction [4].
Several standardized alloys are available which have been optimized
for HPDC processing. Due to their good producibility, cast alloys contain-
ing silicon (EN AC-4xxxx) close to the eutectic composition dominate this
field [5]. A major disadvantage of this alloy class, however, is limited
strength and formability, which limits its use in vehicle body panels. In
particular, lack of ductility makes remedial action necessary to enable
punch riveting operations. Even though AlSi10MnMg, a highly optimized
and very commonly used alloy in crash-relevant applications, offers high
strength due to its age hardenability combined with acceptable ductility,
some efforts have been made to develop and improve AlMg cast alloys
(EN AC-5xxxx). These alloys show a quite attractive combination of mod-
erate strength and increased ductility, including an improvement in cor-
rosion resistance according to their high Mg content [5,6]. On the other
hand, their wide solidification interval makes the casting operation
more difficult and limits the design flexibility of the cast products.
At present, replacing AlSi cast alloys with AlMg cast alloys generates
only minor benefits in final product properties, and is accompanied by
deterioration in processing. Therefore, effort is required to provide
these alloys with better mechanical characteristics. In AlMg wrought al-
loys (EN AW-5xxx), which exhibit the best formability of all aluminum
alloy classes due to their high strain hardening assets (resulting from
the high content of Mg in solid solution), several approaches to increas-
ing their only moderate strength have been investigated [7]. Although
the binary system of Al and Mg shows a thermodynamic tendency of
precipitate formation, non-beneficial kinetics impede a controllable
and favorable use of precipitation hardening by β-Phase (Al3Mg2) and
its precursors, which renders this alloy class non-heat-treatable [4]. In
addition to processing optimizations and alloy development within
the standardized ranges, the deployment and development of precipita-
tion hardening by major alloy modifications with zinc (Zn) and copper
(Cu) have been found to significantly improve the mechanical
properties.
A very early approach by Hino [8] focused on avoiding softening dur-
ing paint baking (175 °C/30 min) by adding 0.5 wt% Cu (KS5030,
KS5032). Precipitation of S′-Phase (Al2MgCu) was found to balance
the softening generated by recovery of the 2% pre-deformed sheets.
Benefits for formability, stress corrosion cracking (SCC) and filiform cor-
rosion have also been reported. More recent investigations on Cu-
modified alloys (EN AW-5182, EN AW-5083) and Cu-containing alloys
(AA 5023) confirm these results. Depending on the thermo-
mechanical treatment, precipitation hardening by S-phase and its pre-
cursors can reduce [9] or even compensate [10] for the decrease in
strength caused by paint bake treatment. Long-term natural aging,
which can be a crucial factor for age hardenable alloys like the 6xxx-
series, showed only a slight increase in strength of only few MPa with-
out any significant effect on ductility in AA 5023 [9]. Studies on
AlMg4.2Cu0.6 by Ratchev [11], which concentrated on the rapid
hardening effect (similar to that of AlCuMg alloys) at early stages of ar-
tificial aging at higher temperatures (180 °C), related the strength in-
crease of approx. 30 MPa to the formation of S″-Phase, which is also
the major hardening component in 2xxx-series alloys [12]. The peak
strength was found to occur after 11 days. Further investigations by
Ratchev [13] focused on the influence of the Cu/Mg ratio (AlMg4.2Cu0.6,
AlMg3Cu0.6, AlMg3Cu0.9) on age hardening behavior. While high Cu/
Mg ratios generate an improvement in the age hardening response
over the whole aging period, low ratios cause a delay in the precipitation
sequence and a minor response. Reducing the aging temperature from
180 °C to 140 °C and a lower Mg content only had a minor effect on
the strength increase in the early stages.
Besides copper, the addition of Zn to AlMg alloys has also been well
reported. In several cases these alloys were treated as 7xxx-series alloys
with very small Zn/Mg ratios (b 1). Age hardening is generated by pre-
cipitation of T-phase (Mg32(Al,Zn)49) and its precursors. The exact de-
scription of the sequence is still disputed, but the difference in crystal
structure and chemical composition between hardening precursors
and equilibrium phase is expected to be only minor [14]. EN AW-7xxx
hardened by T-phase shows higher strength and increased resistance
against intergranular corrosion (IGC) compared to alloys with the
usual Zn/Mg ratios hardened by the η-phase precipitation sequence
[15]. These beneficial effects are also observed in Zn-modified AlMg al-
loys, which exhibit increased corrosion resistance (especially IGC) com-
pared to sensitized 5xxx-series alloys due to the suppression/
modification of the unfavorable β-phase [16–19] and increased strength
caused by precipitation hardening [16,20,21]. Interestingly, serrated
flow due to dynamic strain aging, which is a well-known phenomenon
in 5xxx-series alloys and a result of interactions between solute Mg
atoms and dislocations during deformation [22], is reported to be par-
tially suppressed by adding Zn; this occurs via formation of Zn-Mg clus-
ters during natural aging and precipitate formation during artificial
aging, which causes depletion of solute Mg in the matrix [20,23].
The improved corrosion resistance in both the Cu- and Zn-modified
AlMg alloys led to in-depth investigations on the effect of combined ad-
dition of these elements. It was found that certain amounts of Cu can
balance the impairing effect of Zn on SCC and even improve the me-
chanical properties strength and work hardenability [24–26]. Recently
this kind of modification, with increased alloy content (up to 3 wt% Zn
and 0.45 wt% Cu), has attracted attention due to the significant
strengthening effect by precipitation hardening generated. While Zn-
modified AlMg alloys exhibit a relatively high hardening response
resulting from T-phase and its precursors only after a certain incubation
period, Cu-modified alloys show a rapid hardening effect at early stages
of aging due to GPB-zone formation, but reach moderate peak hardness
resulting from S-phase and its precursors only after longer aging times.
The combined addition of both elements improves the age-hardening
response and leads to higher peak hardness at shorter aging times
through the synergistic effects of T- and S-phase precipitates [27]. The
application of a two-stage artificial aging procedure generates an al-
tered precipitation microstructure and an improved age-hardening re-
sponse compared to single-stage treatment. Peak hardness is caused
by fine and equiaxed precipitates of Cu-modified T-phase [28]. Investi-
gations on the IGC resistance of these alloys have revealed precipitation
free zones (PFZ) at the grain boundaries for alloys containing only Zn,
but also for those alloyed with Zn and Cu. Cu-containing alloys showed
the effects of narrower PFZs and higher density of precipitates in the
grains, which are responsible for higher resistance to IGC [29]. The pre-
cipitation sequence for this kind of alloy seems to depend on the aging
strategy. While at single-stage artificial aging two precipitation mecha-
nisms compete (SSSS (super-saturated solid solution) → GPB-zones → S
″ → S′ → S-phase (Al2MgCu) for the Cu-containing phase and SSSS →
GPI-zones → GPII-zones (T") → T' → T-phase (Mg32(Al, Zn)49) for the
Zn-containing phase), two-stage aging follows the sequence of T-
phase precipitation with the copper atoms incorporated in the T-
phase (Mg32(Al, Zn, Cu)49) [27,28,30].
 L. Stemper et al. / Materials and Design 181 (2019) 107927
Table 1
Main element content of the investigated alloys in wt%.
Mg Mn Zn
Alloy 1 5.0 0.8 3.8
Alloy 2 4.8 0.8 3.4
Taking all this into account, it seems reasonable to determine the ap-
plicability of these measures on cast alloys. If such measures led to sig-
nificant improvements, the trade-off between product properties and
processing would change in favor of AlMg alloys and ultimately result
in a better product. This paper illustrates the results of a systematic
study on the age hardenability of Zn- and/or Cu-modified EN AW-
5083, manufactured by HPDC. The influence of varying both alloying
content and behavior in different heat treatment strategies is a key as-
pect of this study. In addition, the microstructure was analyzed by
TEM investigations to determine the main hardening phases and their
distribution within the grain structure.
2. Experimental
Table 1 presents the main element content of the alloys investigated.
Both are based on EN AW-5083 supplied by AMAG casting GmbH and
modified by adding varying amounts of Zn and Cu.
The alloys were produced at the industrial scale and shed to 3 mm
thick plates with a format of 120 mm × 100 mm by HPDC. Samples
were taken randomly over the casting period and further processed to
hardness samples by cutting and grinding.
A circulating air furnace (Nabertherm N15/65 SHA) was used to per-
form solution annealing at a temperature of 465 °C for 35 min. To gen-
erate a supersaturated solid solution, the samples were quenched by
immersion in water at room temperature or, for the investigation of
quench sensitivity, cooled by air at standard conditions on a wire grid.
While pre-aging and artificial aging at higher temperatures was per-
formed in a circulating oil bath, natural aging took place at room tem-
perature. A full list of all heat treatments investigated, including a
schematic representation, is shown in Fig. 1.
All pictured hardness values in this study represent an average of
five independent hardness measurements which were taken by an
EMCO-TEST M4 unit according to Brinell's method (HBW 2.5/62.5).
Thin-foils for transmission electron microscopy (TEM) were pre-
pared by grinding hardness samples to a thickness of approx. 100 μm.
Punched out 3-mm discs were further processed by twin jet electro-
polishing using a solution of 75% methanol and 25% nitric acid at a
Fig. 1. Schematic representation of the heat treatments and applied parameters.
3
temperature range of −10 °C to −20 °C and a voltage range of 10 V to
20 V. High angle annular dark field (HAADF), bright field (BF) and dif-
Cu fractometry studies were carried out using a FEI Tecnai-F20 HRTEM.
0.0
0.5 3. Results
3.1. Single-step artificial aging at varying temperatures
The hardness change of alloy 1 and alloy 2 during single-step aging
at 125 °C (red lines) and 175 °C (blue dotted lines) are pictured in
Fig. 2a and b, respectively. While no substantial hardening occurs at
175 °C, a remarkable increase in hardness can be observed at the
lower aging temperature of 125 °C for both alloys. The Cu-containing
alloy 2 also exhibits an early aging response after a few minutes and
gains more hardness over the investigated time range than the Zn-
only modified alloy 1. The onset of hardness increase for alloy 1 is also
shifted to longer aging time compared to alloy 2. Peak hardness was
not reached over the aging time studied. Contour-plots indicating the
measured hardness at certain time/temperature-pairings for both alloys
are shown in Fig. 2c and d. It is apparent that temperatures above 150 °C
have hardly any effect on hardness, but that decreasing aging tempera-
ture down to 100 °C accelerates and enhances the hardening response.
Further temperature reduction leads to re-declination of the hardening
rate but still results in high hardness values after longer aging times.
This effect is more distinct in the Cu-containing alloy 2. Again, peak
hardness was not reached at any temperature over the treatment
duration.
3.2. Influence of pre-aging treatments on age-hardening response
The influence of pre-aging was investigated with an eye on two
major aspects: pre-aging duration at 100 °C (according to the highest
hardening rate in single-step aging) and second-step artificial aging
temperature after the most beneficial pre-aging treatment. Hardness
curves for several pre-aging times are plotted in Fig. 3 for alloy 1
(a) and alloy 2 (b). Compared to single-step aging at 150 °C, all pre-
aging treatments (15 min, 60 min and 100 min at 100 °C) show in-
creased hardness at the start but a decrease in strength over the first
couple of minutes of the second aging step, which is more distinct in
the Cu-free alloy 1. While longer pre-aging resulted in an accelerated
and increased hardening response in this alloy, only a minor difference
could be observed when varying pre-aging times in the Cu-containing
alloy 2, even though the level of hardness is higher compared to the
hardness profile without pre-aging treatment. It is also apparent that
4 L. Stemper et al. / Materials and Design 181 (2019) 107927

increased pre-aging time generates enhanced maximum hardness. The
influence of the final aging temperature after 3 h of pre-aging at 100 °C
is plotted in Fig. 3c (alloy 1) and Fig. 3d (alloy 2). Higher temperatures in
the second aging step clearly shift the hardness increase to shorter
times, but also limit the maximum achievable hardness. Pre-aging treat-
ment in combination with increased temperature in the final aging step
also results in over-aging within the observed time interval for both al-
loys. Again, the general hardness level is higher in alloy 2 but a slight
softening is visible at early aging times.
3.3. Natural aging and its effect on age-hardening response
Fig. 4a and b (red lines) shows the evaluation of the stability of the so-
lution treated and quenched condition during natural aging. A clear in-
crease in strength is apparent for both alloys, and Cu alloying seems to
delay the onset to a certain degree but results in a higher hardness at
longer natural aging times. An applied pre-aging treatment (100 °C/3 h)
before natural aging (blue dotted line) generates a higher initial strength
level (especially for alloy 2), but also provides increased stability over at
least 6 days of aging for the Zn-only-modified alloy 1, and over 24 days
for alloy 2. After 175 days at room temperature both the pre-aged and
the non-pre-aged samples exhibit hardness values of 128 HBW and
more, which indicates an undesired strength increase. On the other
hand, two weeks of natural aging after solution heat treatment and
quenching produces the highest values measured during subsequent arti-
ficial aging of all conditions investigated. The hardness profiles for this
heat treatment strategy are pictured in Fig. 4c and d (blue dotted lines)
and compared to single-step aging curves at 125 °C (red line). During
the first 30 s of aging the hardness level resulting from natural aging
stays constant, before dropping almost to the level gained at single-step
aging. With progressive aging time the profile rises again to the highest
values, of 160 HBW for alloy 1 and even 170 HBW for alloy 2.

Fig. 2. Single-step artificial aging of alloy 1 (a) and alloy 2 (b) at 125 °C (red line) and 175 °C (blue dotted line); contour plots of single-step artificial aged alloy 1 (c) and alloy 2 (d) over a
temperature range of 75 °C to 200 °C.
 L. Stemper et al. / Materials and Design 181 (2019) 107927
3.4. Effect of the quenching rate on age-hardenability
In Fig. 5 single-step artificial aging hardness curves (100 °C),
resulting from water quenching (red line) and air cooling (blue dotted
line) after solution heat treatment at 465 °C, are plotted for alloy 1
(a) and alloy 2 (b). Both alloys exhibit noticeable quench sensitivity,
causing significant lower hardness with air cooling applied. This effect
is more distinct for alloy 2.
3.5. Microstructural investigations
The microstructure of both alloys studied was examined with re-
spect to aspects of phase distribution (Fig. 6) and phase identification
(Fig. 7), with a focus on the influence of the heat treatment strategy.
For single-step artificial aging (125 °C/48 h), which represents the al-
most peak aged condition, both alloys show clear appearance of PFZs
and precipitates at grain boundaries. For the Zn-only modified alloy 1
the width of the PFZ exceeds 500 nm (Fig. 6a), but Cu addition (alloy
2) produces a decreased expression of this phenomenon and results in
Fig. 3. Two-step artificial aging of alloy 1 (a, c) and alloy 2 (b, d) with varying pre-aging time (a, b) and varying artificial aging temperature (c, d).
5
a narrower width of approx. 200 nm (Fig. 6b). Within the grain the pre-
cipitates show a fine, uniform distribution for both alloys (Fig. 6e and f),
but they are little coarser and more elongated in the Cu-free alloy 1
(Fig. 6e). This might explain its slightly lower hardness (compare red
lines, Fig. 2a and b).
Two-step artificial aging (100 °C/3 h + 175 °C/3 h), which repre-
sents a fast and thus beneficial age hardening response, generates sig-
nificantly narrower PFZs with widths of approx. 200 nm for alloy 1
(Fig. 6c) and far b100 nm for the Cu-containing alloy 2 (Fig. 6d). It
also generates an increased amount of grain boundary precipitates
(GBPs), as seen in Fig. 6c and d. Compared to single-step aging, two-
step heat treatment produces much smaller precipitates, which appear
in a drastically increased number density of precipitates. Again, the Cu-
containing alloy 2 expresses this effect even more strongly, generating
an explicitly higher hardness level (compare orange dashed line in
Fig. 3c and d).
The diffraction study of both alloys investigated shows a difference
in the presence of hardening phases. A comparison between simulated
diffraction patterns for the phases expected (predicted by Pandat [31],
6 L. Stemper et al. / Materials and Design 181 (2019) 107927
S-phase: Al2MgCu, orthorhombic, aS = 0.400 nm, bS = 0.923 nm, cS =
0.714 nm [11] and T-phase: Mg32(Al,Zn)49, cubic, aT = 1.416 nm, bT =
1.416 nm, cT = 1.416 nm [32,33]) and the experimental data is provided
in Fig. 7. Due to their similar crystal structures a distinction between
precursors and equilibrium precipitation phases was not included in
this study [14,34–36]. Due to the wealth of data in the literature (exper-
imental and theoretical) the experimental results depicted were ac-
quired with the electron beam direction of 〈001〉 to facilitate
evaluation of the diffraction pattern. The alloy without Cu-addition
(alloy 1) exhibits only spots corresponding to T-phase or its precursors
at the 2/5 and 3/5 〈022〉Al position (Fig. 7b), after one-step and two-step
aging [28].
Due to the Cu-addition in alloy 2, the formation of a Cu-rich S-phase
or its precursors is possible. This is indeed observed after single-step ar-
tificial aging treatment. Fig. 7c clearly exhibits additional reflexes at the
predicted position (Fig. 7a) for S-phase between the {002}Al and {022}Al
spots. During the two-step artificial aging process, no S-phase precur-
sors are formed, as can be seen in the corresponding diffraction pattern
Fig. 4. Natural aging of quenched and quenched plus pre-aged alloy 1 (a) and alloy 2 (b). The influence of prior natural aging on subsequent artificial aging at 125 °C of alloy 1 and alloy 2 is
shown in (c) and (d).
(Fig. 7d). This suggests that the precipitation process differs in this alloy
according to whether one-step or two-step aging is applied.
4. Discussion
The results presented in the previous chapter can be summarized by
the following observations:
(i) For single-step aging, it has been found that temperatures above
150 °C only cause a slight hardness increase, while lower temper-
atures significantly increase the hardening response; this is even
more pronounced for the Cu-containing alloy 2. Temperatures
below 100 °C still lead to increased hardness but the onset is
shifted to longer aging times.
(ii) Pre-aging treatments indicate that such procedures can offer su-
perior hardness and kinetics. Increased pre-aging time generates
a higher, accelerated hardness increase. In combination with ele-
vated temperatures in the second aging stage, even greater
 L. Stemper et al. / Materials and Design 181 (2019) 107927
acceleration of the hardening response is possible, but unfortu-
nately this is accompanied by a decreased maximum hardness
level.
(iii) Natural aging after solution heat treatment indicates poor hard-
ness stability at room temperature storage which, however, is
improved by pre-aging treatment. On the other hand, aging at
125 °C after two weeks of prior natural aging generated the
highest hardness values of approx. 160 HBW and 170 HBW for
alloy 1 and alloy 2, respectively.
(iv) The hardening response is significantly influenced by the occur-
rence of quench sensitivity.
We discuss these findings in detail below.
4.1. Single-step artificial aging
According to studies of precipitation behavior in Zn-modified [37]
and Cu-modified [38] AlMg alloys, supersaturated vacancies are bound
to Mg atoms immediately after quenching. Elevated temperatures result
in their gradual release and the formation of clusters which evolve into
precipitates according to the predominant sequence. Due to their obvi-
ous similarities, the alloys of this study are considered to behave in the
same way.
For the Cu-free alloy 1 the supposed sequence is SSSS → GP-zones
(T") → T' → T-phase (Mg32(Al, Zn)49). This agrees well with the phase
identified after aging for 48 h at 125 °C, as no difference is made be-
tween T- and T'-phases due to their similar crystal structures [14,36].
For the Zn- and Cu-containing alloy 2 both T-phase and S-phase were
observed in the same condition. Again, the distinction between S″, S′
and S-phase was not made in this study because of their similar struc-
tures [34,35].
While at early aging times almost no hardening effect occurs at 175
°C for the Zn-only modified alloy 1 (Fig. 2a), a slight increase was mea-
sured for alloy 2 with Cu additions (Fig. 2b). This agrees well with re-
sults found by Cao [27] for aging at 180 °C. They conclude that this
effect might be the result of a favored Mg-Cu cluster formation, which
occurs due to a high diffusivity of Cu and Mg atoms at this temperature.
This, however, leads to a relief in the lattice strain in the solid solution
Fig. 5. Single-step artificial aging at 100 °C of alloy 1 (a) and alloy 2 (b) after water quenching (red line) and air cooling (blue dotted line) after solution heat treatment.
7
and thus to a higher activation energy and larger critical nucleus for
the competing T-phase precursor formation. Once the energy barrier
is overcome, precipitation of the Zn-rich T-phase precursors accelerates
due to the higher diffusion rate of Zn atoms. With consumption of Mg
atoms, the Cu/Mg ratio increases and S-phase precursor formation is fa-
vored again. Peak hardness is gained by synergetic effects of both
phases.
For the lower aging temperature (125 °C) the age hardening re-
sponse in both alloys is much more pronounced, particularly at longer
aging times. For alloy 1 this effect is judged to result from the higher
precipitation pressure caused by higher Mg-supersaturation at lower
temperatures. Provided that Mg is completely in solid solution, i.e. no
solute loss occurs during quenching, thermodynamic calculations
using Pandat [31] predict a Mg-supersaturation of 3.77 wt% at 125 °C
and 3.2 wt% at 175 °C, respectively. The roughly 13% higher supersatu-
ration at the lower aging temperature is assumed to cause both faster
precipitation kinetics of T-phase precursors and an enhanced hardening
response.
Additions of Cu lead to an accelerated and even more enhanced
hardening effect in alloy 2, which is quite unusual for low temperatures.
The diffusivity of Cu atoms is limited at lower temperatures, so T-phase
precursor precipitation is supposed to predominate the S-phase precip-
itation. As both phases were identified clearly after aging at 125 °C for
48 h, it is assumed that Cu somehow promotes the formation of T-
phase precursors as suggested by Cao [29]. With the depletion of Mg
due to the formation of T-phase precursors, the Cu/Mg ratio increases
and S-phase formation is favored. Finally, both phases exist simulta-
neously (Fig. 7c). A high density of precursor phase might also inhibit
the migration of solutes and free vacancies towards grain boundaries,
leading to narrower PFZs and finally resulting in higher hardness
[38,39].
4.2. Two-step artificial aging
A key finding is the fact that applying a pre-aging treatment shifts
the hardening response of the investigated alloys towards an industri-
ally applicable time range.
During pre-aging at lower temperatures (100 °C) it is assumed that
the formation of T-phase precursors is even more pronounced and oc-
curs in higher number densities compared to single-step aging at 125
8 L. Stemper et al. / Materials and Design 181 (2019) 107927

°C. We link this to the increased Mg-supersaturation and the shorter dif-
fusion pathways. Cu additions seem to have an accelerating and
boosting effect on the formation of T-phase precursors, similar to
single-step aging of alloy 2 [28].
Upon subsequent second-stage aging (Fig. 3a and b) previously
formed T-phase precursors may initially dissolve partly, causing a slight
decrease in hardness, but also act as nuclei for rapid hardening at ele-
vated artificial aging temperatures. As can be deduced from Fig. 6e
and g, the high number density of T-phase precursor formed during
pre-aging is obviously inherited by the following second hardening
stage. For alloy 2 the two-step aging is assumed to proceed according
to the same pattern proposed by Cao [28,29], who investigated existing
phases and the distribution of alloying elements by TEM and atom
probe analysis in comparable alloys and heat treatment conditions. Ac-
cording to his experimental results it was stated that Cu atoms are in-
corporated in clusters formed in the first aging step and, therefore, are

Fig. 6. HAADF microstructure of alloy 1 (left column) and alloy 2 (right column) after single-step artificial aging (125 °C/48 h, a, b, e, f) and two-step artificial aging (100 °C/3 h + 175 °C/3 h,
c, d, g, h), PFZ (red arrows).
 L. Stemper et al. / Materials and Design 181 (2019) 107927
no longer available for the formation of S phase precursors. Thus, we
conclude that alloy 2 exhibits a very high number density of solely Cu-
containing T-phase in the peak aged condition (Fig. 7d).
At higher second-step temperatures the hardening response is fur-
ther accelerated, which is attributed to higher diffusion rates of solutes
in the matrix but is also accompanied by decreased peak hardness and
early over-aging resulting from a loss of coherence and an undesired
growth of the hardening phase. PFZ have been found to be less distinct
in the two-step aged condition. This is attributed to the lower diffusion
rates and higher number density of T-phase precursors caused by lower
temperature pre-aging.
4.3. Natural aging
The observed hardness increase at room temperature storage
(Fig. 4a and b) is assumed to be related to a reduction of supersaturation
caused by the formation of clusters, as commonly found in 2xxx-, 6xxx-
and 7xxx-series alloys [40,41]. The effect can be desired or in some cases
also undesired, due to instable mechanical properties in further process-
ing steps. Pre-aging treatment (100 °C for 3 h) shows a retarding effect,
which is more pronounced for the Cu-containing alloy 2. This might be
explained as follows. Due to the low temperature and resulting short
diffusion paths, cluster formation and growth are limited to narrow
spaces, resulting in a high number density of clusters. Likewise, super-
saturation decreases only slowly, so hardening can progress continu-
ously over time. The effect of pre-aging on natural aging can be linked
to the above-mentioned formation of T-phase precursors. It decreases
the supersaturation of cluster-forming elements and thus stabilizes
the microstructure. While only minor differences are found in the natu-
ral aging behavior of alloy 1 and alloy 2, the effect of pre-aging on room
temperature stability seems to be stronger for alloy 2. This can be ex-
plained by the accelerating effect of Cu on the formation of the T-
phase precursors, similar to single-step aging.
Subsequent artificial aging (Fig. 4c and d) after two weeks of natural
aging achieves the highest measured hardening response for both
Fig. 7. Simulated [11] and experimental diffraction patterns with beam direction b001N, Simulated diffraction patterns of S′/S″ (S)-phase (a), alloy 1 after single step aging at 125 °C for 48 h
(b), alloy 2 after single-step artificial aging at 125 °C/48 h (c) and after two-step artificial aging (100 °C/3 h + 175 °C/3 h) (d).
9
alloys. While at the early aging stage previously formed but unstable
clusters may partially dissolve and cause hardness to decrease, continu-
ing aging is slightly accelerated and hardening is intensified. This effect
is thought to be caused by the growth of non-dissolved and, therefore,
stable T-phase precursors, as suggested by Hou [30] for artificial pre-
aging. Interestingly, in contrast to their observations two weeks of nat-
ural aging were able to generate these stable precipitates for the alloys
investigated in this study; Hou found this effect to occur after pre-
aging for 24 h at 90 °C, which may be explained by the different alloy
content. The reason for the extraordinary high strength level after pre-
aging at room temperature might be the higher number density of clus-
ters, and finally precipitates, which evolve from these. A similar effect
can also be found in lean 6xxx-series alloys, where clusters of Si and
Mg solute atoms, which formed during natural aging, are dissolving
only slowly at subsequent artificial aging and/or act as nucleation sites
for further precipitation. [42,43]
4.4. Quench sensitivity
As expected, and typical of 7xxx- and 6xxx-series alloys, the age
hardening response is constrained for slow quenching in air compared
to fast quenching in water [44–46]. The diminished supersaturation of
solutes and vacancies generates a lessened driving force for precipita-
tion of the hardening phase and makes a certain amount of solute un-
available for hardening due to undesired coarse pre-precipitation
while quenching.
5. Conclusions
This study investigated the aging behavior of two precipitation
hardenable AlMg alloys processed via high pressure die casting. The
main conclusions for the AlMgZn and a Cu-added variant are:
• Single-step artificial age hardening is relatively slow and is most ben-
eficial at lower aging temperature around 125 °C. The peak hardness is
10 L. Stemper et al. / Materials and Design 181 (2019) 107927
related to T-phase precursor precipitates and is extended to a higher
level with the additions of Cu, resulting in a second hardening phase
(S-phase precursors).
• Two-step artificial aging can shift the hardening peak into an industri-
ally relevant time range. Longer pre-aging time increases the harden-
ing effect in the second stage. While a lower second-step temperature
increases the hardening response at longer times, a higher tempera-
ture results in a strong acceleration of precipitation but slightly less
distinct strengthening. In peak aged condition, hardening results
from T-phase precursors in both alloys, but it is suggested that T-
phase precursors incorporate certain amounts of Cu atoms for the
Cu-containing alloy, leading to increased strength.
• Natural aging is pronounced and can be retarded by pre-aging, espe-
cially for the Cu-containing alloy. Interestingly, precursors formed
upon natural aging can even generate an extended peak hardening ef-
fect during subsequent artificial aging, compared to the artificial pre-
aging treatments investigated.
The alloys investigated exhibit high potential for future deployment
in light-weight transportation applications.
CRediT authorship contribution statement
Lukas Stemper: Conceptualization, Methodology, Investigation, Visuali-
zation, Writing - original draft. Bernhard Mitas: Investigation, Validation.
Thomas Kremmer: Investigation, Validation, Writing - original draft.
Steffen Otterbach: Supervision. Peter J. Uggowitzer: Conceptualization,
Supervision, Writing - review & editing. Stefan Pogatscher: Project ad-
ministration, Conceptualization, Supervision, Writing - review & editing.
Declaration of Competing Interest
None.
Acknowledgements
Thankfully, this project was funded by the project “SMiLE” initiated
by the German Federal Ministry of Education and Research and Audi
AG. Financial support by the Christian Doppler Research Association,
the Austrian Federal Ministry for Digital and Economic Affairs and the
National Foundation for Research, Technology and Development as well
as AMAG rolling GmbH is gratefully acknowledged. We also thank
Manfred Brabetz for his support in conducting the TEM investigations.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.
CRediT authorship contribution statement
Lukas Stemper: Conceptualization, Methodology, Investigation, Vi-
sualization, Writing - original draft. Bernhard Mitas: Investigation, Val-
idation. Thomas Kremmer: Investigation, Validation, Writing - original
draft. Steffen Otterbach: Supervision. Peter J. Uggowitzer: Conceptual-
ization, Supervision, Writing - review & editing. Stefan Pogatscher:
Project administration, Conceptualization, Supervision, Writing - re-
view & editing.
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