Materials Science & Engineering A 687 (2017) 323–331

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Materials Science & Engineering A

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

Effect of pre-ageing on dynamic strain ageing in Al-Mg-Si alloys MARK

a b c c,⁎ b
Hao Zhong , Paul A. Rometsch , Qianqian Zhu , Lingfei Cao , Yuri Estrin
a
Suzhou Nonferrous Metals Technology Co., Ltd., Suzhou 215026, China
b
Department of Materials Science and Engineering, Monash University, Clayton, VIC 3800, Australia
c
College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China

A R T I C L E I N F O A BS T RAC T

Keywords: The effect of pre-ageing (PA) on dynamic strain ageing (DSA) in Al-Mg-Si alloys with different Mg/Si ratios has
Dynamic strain ageing been studied by using hardness measurements, tensile testing, three dimensional atom probe (3DAP), and
Strain rate sensitivity scanning electron microscopy (SEM). The results show that a pre-ageing step prior to one week of natural
Vacancies ageing promotes DSA and gives rise to a reduced strain rate sensitivity (SRS) of the flow stress. Mechanisms for
Ageing
enhanced DSA are discussed in terms of the 3DAP results. It is concluded that the most likely mechanism for the
Aluminium alloys
observed decrease in the SRS is associated with the presence of excess vacancies promoted by pre-ageing. The
excess vacancies may reside in vacancy-solute complexes (e.g. after pre-ageing at 100 °C for 5 min) or be
trapped in clusters (e.g. after pre-ageing at 100 °C for 2 h).

1. Introduction
Dynamic strain ageing (DSA) and the Portevin-Le Chatelier (PLC)
effect are related phenomena that occur in many dilute alloys [1]. DSA
is a result of dynamic interaction between mobile dislocations and
diffusing solutes [2,3]. The PLC effect is an extreme manifestation of
DSA in the form of discontinuous yielding, which occurs under certain
conditions [2]. The detrimental effect of these phenomena on the
mechanical performance of materials has been known for a long time
[4]. This refers particularly to many aluminium alloys where DSA is
unfortunately a common issue in sheet forming [5]. The reason why
DSA has a detrimental effect on the mechanical performance of a
material lies in a reduction of its strain rate hardening capability.
Indeed, a high strain rate sensitivity (SRS) of the flow stress is required
for good stretch formability [6]. Supersaturation of solutes and
vacancies can promote the development of DSA [7]. Moreover, the
PLC effect occurs when the SRS of the flow stress is below a certain
level in the negative range of SRS, which suggests a strong DSA
mechanism is operating [1].
In the ongoing quest for car weight reduction, the 6xxx series Al-
Mg-Si alloys are considered among the most promising candidates for
aluminium automotive body panel applications [8]. After solution
treatment and pre-ageing, they are shipped and formed while still
formable and are subsequently subjected to a paint-bake cycle to
increase their strength by age hardening. The purpose of pre-ageing is
to reduce the known negative effect of natural ageing (during the
delivery and storage of the sheets) on the paint-bake performance [9].
It has been reported that pre-ageing can retard clustering of solute
atoms during subsequent natural ageing and thereby improve the
paint-bake performance [9,10]. It is generally accepted that clusters
formed during pre-ageing will nucleate hardening precipitates during
the paint-bake cycle more readily than clusters formed during natural
ageing do [11]. Furthermore, pre-ageing is also expected to influence
the vacancy and solute concentrations in solution, which can influence
the occurrence of DSA and the PLC effect. Although DSA and the PLC
effect were studied in artificially aged 6xxx alloys [7], little attention
was paid to DSA in pre-aged 6xxx alloys naturally aged subsequently –
a processing schedule, which is close to the industrial production of
automotive sheet from 6xxx alloys. Natural ageing after pre-ageing is
expected to further influence the solute and vacancy concentrations in
the alloy, which, in turn, affects DSA. In order to investigate how pre-
ageing and subsequent natural ageing influence DSA, in this work two
6xxx alloys were studied systematically. By designing one alloy with
excess Si and the other with excess Mg, both having the same total
atomic percentage of Mg and Si, it was possible to gain further insights
into the relative effects of Mg and Si.
2. Experimental procedure
The compositions of the two alloys studied are shown in Table 1. As
mentioned above, it is essential that the total atomic percentages of Mg
and Si in the Mg-excess alloy A2 and the Si-excess alloy A4 were nearly
the same. We will provide a detailed analysis on DSA in the high Mg
content alloy A2, and then use the proposed mechanism to explain

⁎
Corresponding author.
E-mail address: caolingfei@cqu.edu.cn (L. Cao).

http://dx.doi.org/10.1016/j.msea.2017.01.051
Received 19 October 2016; Received in revised form 14 January 2017; Accepted 18 January 2017
Available online 19 January 2017
0921-5093/ © 2017 Elsevier B.V. All rights reserved.
H. Zhong et al. Materials Science & Engineering A 687 (2017) 323–331

Table 1
Alloy composition.

Alloy Fe Mn Ti Mg Si Mg/Si Mg+Si

wt% wt% wt% wt% at% wt% at% atomic ratio at%

A2 0.07 0.12 0.10 1.06 1.18 0.50 0.48 2.46 1.66

A4 0.07 0.12 0.11 0.41 0.46 1.26 1.21 0.38 1.67

what we found about the DSA in the high Si content alloy A4.
Ingots were cast into permanent moulds, homogenised at 460 °C
for 6 h and then at 540 °C for 24 h. The homogenised ingots were hot
rolled from 46 mm to 6 mm with 10–30% thickness reductions in each
pass, and then cold rolled to 1 mm with thickness reductions for each
pass similar to that in hot rolling.
The sheets were solution treated at 550 °C for 30 min in a salt bath, Fig. 1. Illustration of the results of a strain-rate jump test for alloy A4.
followed by water quenching (a condition designated ‘Asq’, for ‘as-
quenched’). The as-quenched samples were divided into two groups.
Samples of the first group were naturally aged (NA) for one week
(NA1w) or one month (NA1m); samples of the second group were
immediately (i.e. straight after water quenching) pre-aged (PA) at
100 °C for 5 min (PA5min), 30 min (PA30min), 1 h (PA1h), 2 h
(PA2h), or 4 h (PA4h), followed by natural ageing for one week. After
these treatments, all samples were isothermally aged at 170 °C for
30 min to simulate the paint-bake schedule used in automotive
applications (designated as PB). For comparison, some pre-aged
samples were also naturally aged for one month. In addition, alloy
A2 was naturally aged for 1 h (NA1h) or 24 h (NA1d) after quenching.
The grain structure of the solution treated alloys was studied by
scanning electron microscopy (SEM) using a JEOL-JSM-6480 with
electron backscattered diffraction (EBSD). The microstructures of the
solution treated alloys were studied using a field emission gun SEM
(JEOL 7001F). Three-dimensional atom probe (3DAP) experiments
Fig. 2. Effect of pre-ageing time at 100 °C on the hardness of alloy A2.
were carried out on a CAMECA LEAP 4000 h type local electrode atom
probe. The needle samples were probed at a temperature of 20 K with a
3. Results
pulse fraction of 20%, a pulse rate of 200 kHz and a detector efficiency
of 36%. Visualisation and analysis of the 3DAP data were carried out
3.1. Hardness
using IVAS™ 3.6.12 software. The input parameters for the cluster
detection process were determined both from the literature and from
The effect of the pre-ageing time on the hardness of high Mg
atomic reconstruction results, where the minimum number of solute
content alloy A2 is presented in Fig. 2. Three regimes were considered:
atoms (Nmin) was set to 10, the maximum distance between atoms
(i) pre-ageing (PA) at 100 °C; (ii) pre-ageing at 100 °C followed by one
(Dmax) was set to 0.7 nm, and the surround distance (L) and the
week of natural ageing (PA+NA1w); and (iii) the schedule described in
erosion distance (S) were chosen to be the same as Dmax for a
(ii) with a subsequent paint baking (PA+NA1w+PB) treatment. It can
reasonable detection of nearest neighbor atoms. The volume fraction
be seen that pre-ageing at 100 °C can significantly enhance the paint-
represented the combined value of detected Mg and Si atoms in
bake response of the alloys after one week of natural ageing, compared
clusters divided by the sum of all detected atoms within the volume
to the paint-bake response of the material without pre-ageing. The
analysed.
hardness, measured immediately after pre-ageing, rises with increasing
Hardness testing was carried out on the alloys in the different
pre-ageing time. After subsequent one week of natural ageing, the
conditions by using a Vickers hardness tester with a 5 kg load and an
hardness of the pre-aged samples was observed to drop first, and then
indentation time of 15 s. The mean value for five impressions was taken
to increase gradually with increasing pre-ageing time. The overall
as the hardness of the corresponding condition, and the magnitude of
result is a decrease in natural ageing response after pre-ageing with
the standard deviation was chosen for the error bars in the graphical
growing pre-ageing time. Particularly, after pre-ageing for two hours or
representation of the results. Conventional uniaxial tensile tests and
more, there is almost no natural ageing response during further room
strain rate jump tests were conducted on pre-aged and naturally aged
temperature storage. In other words, the material is very stable after
samples. The gage length of tensile samples was 10 mm. To determine
pre-ageing in terms of hardness. Furthermore, the paint-baked hard-
the uniaxial tensile properties, an Instron 4505/5500 R screw-driven
ness increases with the duration of pre-ageing, but this increase tends
tensile machine was used at a nominal strain rate of 2×10−3 s−1. Strain
to saturate after pre-ageing times of about one hour.
rate jump tests were performed with the strain rate being changed by a
factor of 10, typically between nominal strain rates of 2×10−4 s−1 and
2×10−3 s−1. The extrapolation used to calculate the SRS given by 3.2. Tensile results
• •
log(σ2 /σ1)/ log(ε2 / ε1) [12], is defined in Fig. 1. The average values of
the tensile data from three samples were reported for each alloy. The Typical stress-strain curves for alloy A2 pre-aged at 100 °C for
maximum and the minimum values were taken for the upper and lower different times are shown in Fig. 3. It can be seen that, with increasing
points of the error bars, respectively. pre-ageing time, discontinuous yielding gradually disappeared. This is
consistent with the results reported in [7].

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Table 2
Mechanical properties and absorbed energy obtained from tensile curves.

Tempers Tensile Yield Elongation (%) Absorbed

strength strength energy (J/mm3)
(MPa) (MPa)

NA1w 251 136 33.8 0.078

PA5min 230 118 32.6 0.067
+NA1w
PA30min 219 106 33.3 0.065
+NA1w
PA1h 226 114 33.6 0.069
+NA1w
PA2h 232 121 30.8 0.064
+NA1w
PA4h 237 127 33.6 0.072
+NA1w

Fig. 3. Engineering stress-strain curves for alloy A2 aged at 100 °C for different times.
the alloy in NA or PA+NA conditions. The energy absorption data is
presented in Table 2, along with other mechanical properties. It can be
seen that pre-ageing slightly diminishes the strength and the tensile
elongation, thus causing a minor drop in the absorbed energy.

3.3. Microstructure

As a reference, the microstructure is shown for alloy A2 only since it

is broadly similar to that of alloy A4. The grain structure of solution
treated alloy A2 is shown in Fig. 6. The average grain size was
measured to be 34 µm. It is noted that after solution treatment,
undissolved coarse particles, mainly Mg2Si and Al(Fe,Mn)Si particles,
were observed in the microstructure (see Fig. 7).
During pre-ageing or subsequent natural ageing, solute-containing
clusters may be formed. A potent technique to detect such clusters,
which was used in this study, is 3DAP. Fig. 8 shows a 3D representation
of the solute clusters in the A2 alloy for NA1w, PA2h+NA1w and PA4h
Fig. 4. Engineering stress-strain curves for alloy A2 after one week of natural ageing
+NA1w conditions. A significant decrease of the volume fraction of
without pre-ageing or with pre-ageing for different times.
clusters in the case when prior pre-ageing is applied (PA2h+NA1w) is
evident. However, when the prior pre-ageing time is increased (PA4h
+NA1w), the volume fraction of clusters is increased as well.
Quantitative analysis of 3DAP data summarised in Table 3 indicates
that the percentage of solutes remaining in the matrix is still in excess
of 92%, and it does not follow the variation of the pre-ageing time. The
fraction of solute Si and Mg in clusters does decline after the prior pre-
ageing treatment of 2 h, but it increases with another 2 h of prior pre-
ageing. That is to say, the solute concentration varies slightly across
different tempers, while most of the solute content remains in the
matrix.

4. Discussion

Pre-ageing is supposed to deplete the bulk of an alloy of solutes and

Fig. 5. Effect of pre-ageing and natural ageing on the SRS of the flow stress of alloy A2.
It is remarkable, that upon one week of natural ageing that followed
pre-ageing serrated yielding was still found in PA+NA1w samples, even
after prolonged pre-ageing for 4 h at 100 °C (Fig. 4). By contrast, the
stress-strain curve for NA1w sample was smooth (Fig. 4). Based on the
relationship between the PLC effect and the SRS of the flow stress
described in the Introduction, the serrated yielding in PA+NA1w
suggests a more negative strain rate sensitivity (SRS) than that in the
NA1w sample (especially at strains close to 0.02 and higher than 0.1),
as shown in Fig. 5.
Furthermore, the energy absorbed during tensile tests was calcu-
lated by measuring the area underneath the stress-strain curves [13–
15]. This characteristic may provide useful information for stamping of
excess vacancies. This depletion inhibits dynamic strain ageing.
Therefore, the PA+NA1w samples are expected to exhibit a higher
SRS of the flow stress than NA1w samples. Accordingly, serrated
yielding (or the PLC effect) should be more pronounced in the NA1w
samples. However, an opposite trend was observed: the tendency for
serrated yielding became weaker and gradually disappeared with
increased pre-ageing time, due to the depletion of solutes and vacancies
(as shown in Fig. 3). This suggests a higher SRS in PA samples than in
as-quenched sample. However, after one week of natural ageing, the
SRS of PA+NA1w samples was observed to be lower than that of NA1w
samples. The PLC effect was observed in PA+NA1w samples, but not in
the NA condition. This suggests that natural ageing that followed pre-
ageing has an important effect on the SRS of PA+NA1w samples.
To rationalise these effects, two factors that can influence the SRS of
the flow stress should be considered. These are strengthening due to
dislocation-dislocation interactions and dynamic strain ageing asso-

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Fig. 6. EBSD grain structure of solution treated alloy A2.

Table 3
3DAP results for alloy A2 in different tempers.

Temper Percentage of solutes remaining in the Volume fraction of

matrix (%) clusters (%)

Si Mg

NA1w 94.0 93.6 0.142

PA2h+NA1w 97.2 98.1 0.095
PA4h+NA1w 92.7 94.6 0.157

Fig. 7. Backscattered electron image showing undissolved coarse particles in the

solution treated alloy A2.

ciated with dislocation-solute interactions [16]. The first mechanism is

related to cutting of dislocation forest junctions by mobile dislocations,
and is expected to give a positive contribution to the SRS. The second
mechanism involves a negative contribution of the SRS stemming from
DSA. Therefore, the decreased SRS in the PA+NA1w samples may be
caused either by reduced strengthening due to dislocation-dislocation
interaction or by increased DSA.

Fig. 9. Effect of pre-ageing time on strengthening by dislocation-dislocation interaction

4.1. Strain hardening analysis
at a strain of 0.02 in pre-aged alloy A2 after one week of natural ageing.

The detailed study showed that pre-ageing has little influence on

of 0.02 was chosen as a representative value because the difference in
the strain hardening. This is reflected in the difference between the flow
the SRS at a strain of 0.02 was significant across the different tempers.
stress and the yield strength being small, which is a signature of small
A lack of any notable influence of pre-ageing on the strain hardening
strain hardening, cf. Fig. 9. It can thus be conjectured that the
behaviour of the alloys is also seen in Fig. 10 representing the strain
decreased SRS in PA+NA1w samples should be caused by an increased
dependence of the strain hardening rate.
negative DSA contribution. It should be noted that the SRS at a strain

Fig. 8. Atom maps of detected clusters for alloy A2 in different heat treatment conditions. Green and blue dots represent Mg and Si atoms, respectively. All boxes are of the same size of
20×20×100 nm3 to facilitate visual comparisons. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

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H. Zhong et al.
Fig. 10. Strain hardening rate vs. plastic strain for alloy A2 in different tempers.
4.2. Dynamic strain ageing analysis
In interpreting an increased DSA and related PLC effect, it should
be considered that these effects are likely caused by an interaction
between mobile dislocations and diffusing solutes (as in classical PLC
effect) or by repeated shearing of shearable clusters/precipitates
(‘pseudo PLC’ effect) [17].
Hence, two possible mechanisms are proposed for the increased
DSA and observed PLC effects:
1) PA+NA1w samples may contain more solutes/vacancies than NA1w
samples, which causes a greater DSA effect in the former. The
excess solutes/vacancies decrease the SRS, and thus, promote the
occurrence of the serrated yielding (Mechanism I). However, the
3DAP results for alloy A2 suggest that the solute concentration
difference in the matrix is small across different tempers, as
documented in Table 3. This would suggest, for a specific alloy
and for the conditions tested, the solute concentration in the bulk
might not be so critical for the DSA. Thus, the importance of
vacancies for the DSA can be highlighted. However, the question of
where those excess vacancies in the PA samples are located then
needs to be answered. It is known that immediately after quenching
there is a high concentration (an atomic fraction of 10−5–10−4) of
non-equilibrium vacancies in the alloys considered [18]. Unlike in
pure metals, where these vacancies rapidly annihilate at free
surfaces, in alloys containing typically 1–2 at% of solute atoms
such as Mg and Si, solute-vacancy complexes are formed very
quickly [18]. As suggested by Banhart et al. [19], after an extended
period of natural ageing of 6xxx alloys, a majority of those vacancy-
solute complexes will transform to vacancy-free co-clusters. If a
6xxx alloy is pre-aged for, say, 30–60 s at 180 °C, solute clusters are
expected to form during pre-ageing [20]. Any solute-vacancy
complexes remaining after pre-ageing are expected to either form
new clusters or join existing clusters [21]. This process of forming
new clusters or joining existing clusters would be retarded due to a
reduction in both solute and/or vacancy concentration by pre-
ageing so that, after one week of natural ageing, the concentration
of solute-vacancy complexes in the pre-aged samples may be higher
than in the absence of pre-ageing. The concentration of excess
solute-vacancy complexes in PA+NA1w samples may still be low,
yet sufficient enough for promoting the interaction between mobile
dislocations and diffusing solutes, thereby reducing the SRS as
observed in Fig. 5. Moreover, the excess complexes in PA+NA1w
samples are expected to produce a more significant natural ageing
response than in NA1w samples, if both kinds of samples are
further naturally aged beyond the one week of natural ageing (e.g.
one month of natural ageing). Longer natural ageing following pre-
ageing should increase the SRS of the flow stress due to further
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Materials Science & Engineering A 687 (2017) 323–331
removal of solute-vacancy complexes from the matrix and the
ensuing reduction of the DSA contribution to the stress. In fact,
Takaki et al. [22] also found that pre-ageing can impede the natural
ageing process within one week of NA. After that time, natural
ageing became significant, so that the hardness of PA+NA samples
was higher than that of NA samples. No mechanism for these
finding was proposed, though. In another study, Pogatscher et al.
[23] found that after interrupted quenching (a process similar to
pre-ageing), 6xxx alloy samples can exhibit an enhanced artificial
ageing response. It was suggested that quenched-in vacancies
required for the formation of hardness-enhancing precipitates are
not available after standard water quenching and long-term natural
ageing, but can be provided during interrupted quenching in the
right temperature region (i.e. 160 °C) [23]. The findings of
Pogatscher et al. [23] support our view that, after natural ageing,
pre-aged samples should contain more mobile solute-vacancy
complexes than samples that did not undergo pre-ageing. This
could be partly due to the equilibrium vacancy concentration at
100 °C being about two orders of magnitude higher than that at
room temperature. The sluggish NA after pre-ageing would thus
inhibit the development of the vacancy concentration towards its
equilibrium value at room temperature, leading to higher vacancy
concentration in PA+NA1w than in NA1w samples. Hence, the SRS
of PA+NA1w samples should be lower than that of NA1w samples.
The decreased SRS promotes the occurrence of the serrated yielding
in the high Mg content alloy A2, as was observed experimentally.
Alternatively, excess vacancies may be trapped in clusters
formed during pre-ageing, as suggested by Abouarkoub et al.
[24]. The trapped excess vacancies would not contribute to the
natural ageing process after pre-ageing regardless of the duration of
subsequent natural ageing. However, those excess vacancies can
still contribute to the development of DSA if vacancy-containing
clusters are sheared by mobile dislocations, and vacancies are
thereby released from clusters into the bulk.
2) PA+NA1w samples may contain a higher volume fraction of
clusters/precipitates than NA1w samples. Repeated shearing of
these shearable clusters/precipitates by gliding dislocations may
give rise to discontinuous yielding (Mechanism II). However, it
appears that 3DAP results (see Table 3) only support this mechan-
ism for samples that were pre-aged for 4 h. Moreover, if Mechanism
II is operating, one may expect that the SRS of pre-aged samples
should not increase if pre-aged samples are further naturally aged
for one month, since additional clusters are expected to form during
the natural ageing stage.
In order to test the validity of these two hypothetical mechanisms,
alloy A2 was naturally aged for either one week or one month after pre-
ageing. Although the natural ageing effect was retarded during one
week of natural ageing after pre-ageing, it was more pronounced in the
pre-aged samples during one week to one month of natural ageing if
the samples were pre-aged at 100 °C for less than 2 h (see Fig. 11). This
result is consistent with the findings of Takaki et al. [22]. However, it is
interesting to see that the natural ageing response during one week to
one month of natural ageing is almost the same for the samples pre-
aged for more than 2 h and non pre-aged samples. Furthermore, the
hardness results in Fig. 11 suggest that one month of natural ageing
has a more significant effect on the SRS of the flow stress of the samples
pre-aged for a short time (e.g. 5 min) than on that of the alloys pre-
aged for a long time (e.g. 2 h). In fact, after one month of natural
ageing, discontinuous yielding disappeared in alloy A2 samples that
were pre-aged for 5 min. By contrast, discontinuous yielding was still
present after one week of natural ageing of alloy A2 pre-aged for 5 min,
as shown in Fig. 12a. It should be noted, however, that one month of
natural ageing did not have any significant effect on the discontinuous
yielding observed in alloy A2 pre-aged for 2 h, although it appears the
onset strain for the serrations increased slightly with increasing natural
H. Zhong et al.
Fig. 11. Effect of pre-ageing and natural ageing on the Vickers hardness of alloy A2.
ageing time, as shown in Fig. 12b. An improvement (that is, an
increment) in strain rate sensitivity (at a strain of 0.02) by longer
natural ageing was more significant in samples pre-aged for 5 min than
in those pre-aged for 2 h, as shown in Fig. 13. (It should be noted that
due to the serrated yielding, the uncertainty for the SRS determination
becomes large. Therefore, the SRS results from three tests for both
conditions involving pre-aging are presented in Fig. 13 to illustrate the
scatter in the data.) These results support Mechanism I as a cause for
the decrease in the SRS in the PA+NA1w samples. With increasing pre-
ageing time, one would expect a higher volume fraction of vacancy-
containing clusters capable of nucleating hardness-enhancing precipi-
tates, and hence a diminished propensity for cluster formation during
the subsequent natural ageing in the NA1w or NA1m regimes. The
strain hardening behaviour of pre-aged alloy A2 with subsequent
different NA time was also analysed. As shown in Fig. 14, NA that
followed PA has little effect on the strain hardening rate of the alloys.
This result highlights the importance of DSA, showing that the role of
DSA in the SRS of the flow stress is greater than that of strain
hardening.
For longer pre-ageing times (i.e. not less than 4 h at 100 °C), there
are indications that Mechanism II is operating. In this case, the
increased tendency for discontinuous yielding may be caused by
repeated shearing of clusters formed during pre-ageing, which was
suggested to be the underlying mechanism for the observed serrations
on the deformation curves for Al-Li alloys [17].
With regard to Mechanism I, it is still unclear why after one week of
natural ageing pre-aged samples would contain more vacancies than
non pre-aged ones. To rationalise that, it is useful to consider the
natural ageing behaviour of the alloy when there is no pre-ageing
Fig. 12. Effect of natural ageing on the stress-strain curves of alloy A2 pre-aged (a) at 100 °C for 5 min and (b) at 100 °C for 2 h.
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Materials Science & Engineering A 687 (2017) 323–331
involved (i.e. natural ageing starts right after quenching from the
solution treatment temperature). Several points can be put forward
about the natural ageing behaviour of these alloys:
• The PLC effect can be observed remarkably well in as-quenched
samples. As the natural ageing proceeds, the PLC effect gradually
disappears due to the depletion of solutes/vacancies from solution
(see Fig. 15a). The depletion of vacancies is particularly important
for the disappearance of the PLC effect, since based on 3DAP results
most of Mg and Si content (around 80%) was still retained in
solution after one month of natural ageing [25].
• If the natural ageing process after quenching is sluggish (or
suppressed altogether), then it should take more time for the
removal of vacancies from the matrix to occur, and thus more time
for the PLC effect to disappear. For instance, a low Mg content 6xxx
alloy (Al-0.43Mg-0.45Si) with retarded natural ageing still showed
discontinuous yielding after one day of natural ageing (although the
PLC effect disappeared after one week of natural ageing) [26], as
shown in Fig. 15b. By contrast, alloy A2 (high Mg content) with a
greater natural ageing response did not show discontinuous yielding
already after one day of natural ageing (Fig. 15a). One would expect
the classical PLC effect to be more significant in the higher Mg alloy
A2. However, an opposite trend was observed, which highlights the
important role of the retarded natural ageing on DSA.
Based on the above experimental findings, natural ageing can be
considered as a process of formation of solute clusters and removal of
vacancies from the alloy (with their annihilation at free surfaces or
grain boundaries), as suggested by Banhart [18]. If the natural ageing
process after quenching is retarded or entirely suppressed, then both
the formation of clusters and the removal of vacancies during natural
ageing are expected to be inhibited. This would suggest that samples
have to be naturally aged longer to remove more vacancies. This
explains why the alloys with a sluggish natural ageing response did
show serrated yielding after a certain natural ageing time, while those
with a fast natural ageing response did not.
Now the situation with the pre-aged alloys is considered. After pre-
ageing, vacancy concentration is decreased (however, it should be
noted that equilibrium vacancy concentration at pre-ageing tempera-
ture should be still higher than that at room temperature, even though
pre-ageing can decrease vacancy concentration), compared to that in
as-quenched condition. The decreased vacancy concentration would
suppress the subsequent natural ageing process, and thus delay the
annihilation of mobile complexes, so that, after one week of natural
ageing, vacancy concentration in PA+NA1w samples is higher than
NA1w samples. Based on the modelling results [27], after one week of
natural ageing, the vacancy concentration in NA1w samples should
reach the equilibrium level. That is to say the vacancy concentration in
H. Zhong et al.
Fig. 13. Effect of natural ageing on the SRS of the flow stress of alloy A2 pre-aged at 100 °C for (a) 5 min and (b) 2 h.
Fig. 14. Strain hardening rate curves for pre-aged alloy A2 with different subsequent NA time.
PA+NA1w samples should be higher than the room temperature
equilibrium concentration. This high vacancy concentration may lead
to a lower SRS in the PA+NA1w condition than in the NA1w one, and
possibly even give rise to the occurrence of the PLC effect in PA+NA1w
samples. In this case, excess vacancies are supposed to be solute-
vacancy complexes, thus led to a higher natural ageing response if PA
+NA1w samples and NA1w samples were both further naturally aged
for 1 month. This mechanism can account for the observed phenom-
enon when samples are pre-aged for less than 2 h.
If pre-ageing is conducted for a longer time (i.e. more than 2 h), the
excess vacancies are supposed to be trapped in clusters. Therefore, no
significant natural ageing response after extended pre-ageing can be
expected, regardless of the duration of subsequent natural ageing. The
shearing of vacancy-containing clusters during deformation would
release excess vacancies, and thus promote DSA, which, in turn, would
lead to a drop in the SRS and the occurrence of serrated yielding.
The above considerations suggest that the somewhat exotic
Mechanism II may be at play under certain conditions. For instance,
it was established that the volume fraction of clusters/precipitates in
PA+NA samples was higher than that in NA samples when they were
pre-aged for a long time (i.e. 4 h). However, the more conventional
DSA-based processes are believed to be the major cause of discontin-
uous yielding in alloy A2. In this picture, as the natural ageing response
declines, the amount of DSA increases (chiefly because more complexes
are retained after one week of natural ageing). Consequently the SRS
should become more negative (provided Mechanism I is not sensitive
to the pre-ageing time).
Finally, the key findings of this work are as follows: the SRS of the
flow stress of pre-aged samples with subsequent natural ageing is lower
than that of samples that were just naturally aged. The decrease in the
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Materials Science & Engineering A 687 (2017) 323–331
SRS even leads to the occurrence of the PLC effect in pre-aged alloy A2
(high Mg content) with subsequent natural ageing, while no PLC effect
was observed when the alloy was just naturally aged. This result is
unexpected since PA is considered to deplete the supersaturation of
solutes and vacancies in the matrix, and therefore the SRS after PA
+NA1w should be higher than after NA1w only. (Note: a high
concentration of solutes and vacancies should lead to a low or even
negative SRS).
One proposed mechanism (Mechanism I) is summarised as follows:
after one week of natural ageing, pre-aged samples contain more
vacancies than samples that did not undergo pre-ageing. This is due to
a sluggish natural ageing caused by pre-ageing, which delays the
removal of vacancies from the matrix. The excess vacancies enhance
the DSA mechanism, thus diminishing the SRS and promoting the
occurrence of the PLC effect. The excess vacancies may occur as
vacancy-solute complexes or be trapped in solute clusters depending
on pre-ageing time. For a short pre-ageing time (i.e. no more than 2 h),
the excess vacancies are likely to reside in complexes. In contrast, for a
long pre-ageing time (i.e. longer than 2 h), the excess vacancies most
probably occur as trapped-in vacancies in solute clusters. The shearing
of such clusters during deformation releases vacancies, thus increasing
the magnitude of DSA and reducing the SRS. It should be noted that for
a long pre-ageing time (say, more than 4 h), Mechanism II may be
operating provided the volume fraction of clusters formed during pre-
ageing exceeds that of clusters formed during natural ageing only.
Repetitive shearing of clusters formed during pre-ageing can provide a
negative contribution to the SRS and promote the occurrence of
serrations (‘pseudo-PLC’ effect).
Furthermore, Mechanism I is also found to be relevant for the high
Si content alloy A4. As shown in Fig. 16, PA+NA1w samples showed a
H. Zhong et al.
Fig. 15. (a) Engineering stress vs. strain plots for alloy A2 in different natural ageing
conditions and (b) engineering stress vs. strain plot for Al-0.43Mg-0.45Si after one day of
natural ageing.
Fig. 16. Effect of pre-ageing and natural ageing on the SRS of the flow stress of alloy A4.
lower SRS than NA1w ones (although no PLC effect was observed for
PA+NA1w samples, as shown in Fig. 17), due to a higher vacancy
concentration in the former. This high vacancy concentration resulted
in a stronger natural ageing response if PA+NA1w samples were
further naturally aged for one month, as shown in Fig. 18.
The reasons why the PLC effect can be observed in PA+NA1w alloy
A2, but not in high Si content alloy A4, are as follows:
1) The characteristic waiting time of dislocations at pinning points is
comparable with the characteristic time of diffusion of Mg atoms to
temporarily pinned mobile dislocations. This makes DSA more
significant in the high Mg content alloy A2 than in the high Si
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Materials Science & Engineering A 687 (2017) 323–331
Fig. 17. Engineering stress-strain curves for alloy A4 after one week of natural ageing
without pre-ageing or with pre-ageing for different times.
Fig. 18. Effect of pre-ageing and natural ageing on the Vickers hardness of alloy A4.
Fig. 19. The dependence of the SRS on the true strain for alloys A2 and A4 after pre-
ageing at 100 °C for 1 month.
content alloy A4. As shown in Fig. 19, even after ageing at 100 °C
for 1 month, DSA is still observable in alloy A2, which manifests
itself as a decrease in the SRS with increasing strain.
2) One should realise that a low SRS does not ensure the occurrence of
the PLC effect. The serrated yielding only occurs when the SRS
decreases to a finite negative value [26], i.e.
SRS < − (Θ − σ )Ω (1)
−4
where Ω is a strain dependent quantity with an order of 10 . In this
H. Zhong et al.
Fig. 20. The dependence of (Θ-σ) on the true strain of the pre-aged (at 100 °C for 2 h)
alloys after one week of natural ageing.
study, Ω was assumed to be constant across different alloys. In other
words, only the (Θ-σ) term was considered for the occurrence of the
PLC effect. The dependence of (Θ-σ) on the true strain of the pre-aged
alloys is shown in Fig. 20. It is not surprising that the PLC effect was
more readily observed in the high Mg content alloy A2 than in the high
Si content alloy A4, since the high Mg alloy exhibits lower (Θ-σ) levels
than the high Si one.
5. Conclusions
The effect of pre-ageing (PA) on the strain rate sensitivity (SRS) of the
flow stress of two 6xxx alloys with either high Mg (A2) or high Si (A4), but
the same combined Mg+Si content, was studied. It was found that:
(1) The SRS of the flow stress for samples naturally aged for one week
(NA1w) is higher than that for samples with prior pre-ageing (PA
+NA1w).
(2) The decrease in SRS for PA+NA1w samples is associated with
enhanced dynamic strain ageing, which can be caused by excess
vacancies. For short pre-ageing times (e.g. less than 1 h at 100 °C),
excess vacancies exist as vacancy-solute complexes, which are
mobile and can enhance DSA directly. For long pre-ageing times
(e.g. 2 h at 100 °C), excess vacancies are mainly trapped in
clusters; they can be released by shearing and thus promote DSA.
(3) For a further prolonged pre-ageing (e.g. not less than 4 h at
100 °C), the pseudo-PLC mechanism may also be operating. In
this case, clusters formed during pre-ageing are predominant over
those emerging during natural ageing. The decreased SRS in PA
+NA1w samples is caused by the repeated shearing of these
clusters, whose volume fraction is larger in this case (which
involves pre-ageing) than in the NA1w condition.
(4) For the high Mg content alloy A2, this decrease of SRS by pre-
ageing even leads to the occurrence of the PLC effect in the PA
+NA1w condition, unlike in the NA1w material. For the high Si
content alloy A4, neither NA1w nor PA+NA1w samples exhibited
the PLC effect. This difference between alloys A2 and A4 is
attributed to a stronger dynamic interaction of dislocations with
Mg atoms than with Si atoms.
Acknowledgements
The authors thank the Aluminum Corporation of China Ltd.
(Chalco) for supporting this work financially and for providing
materials through the Australia-China International Centre for Light
Alloys Research (ICLAR). Seminal input from Profs. Ian Polmear and
Barry Muddle in alloy selection is gratefully appreciated. The National
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Materials Science & Engineering A 687 (2017) 323–331
Key Research and Development Program of China (2016YFB0300901)
and Project 51421001 supported by the National Natural Science
Foundation of China for L.F. Cao are acknowledged.
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