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Acta Materialia 72 (2014) 125–136
www.elsevier.com/locate/actamat

Atomic-scale analysis of the segregation and precipitation

mechanisms in a severely deformed Al–Mg alloy
X. Sauvage a,⇑, N. Enikeev b,c, R. Valiev b,c, Y. Nasedkina a, M. Murashkin b,c
a
University of Rouen, CNRS UMR 6634, Groupe de Physique des Matériaux, Faculté des Sciences, BP12, 76801 Saint-Etienne du Rouvray, France
b
Institute for Physics of Advanced Materials, Ufa State Aviation Technical University, K. Marx 12, Ufa 450000, Russia
c
Saint Petersburg State University, Universitetsky Prospect, 28, 198504 Peterhof, St Petersburg, Russia

Received 31 January 2014; accepted 15 March 2014

Available online 19 April 2014

Abstract

Due to their interaction with crystalline defects, solute atoms play a critical role in the microstructure evolution of aluminum alloys
during deformation. In addition, deformed structures often exhibit a modified aging response. For a better understanding of these
mechanisms, we provide here a thorough study of deformation-induced segregation and precipitation mechanisms in an aluminum alloy
containing 5.8 wt.% Mg subjected to severe plastic deformation (SPD). The solutionized alloy was processed by high-pressure torsion at
room temperature and at 200 °C. The investigation of the microstructure and of the distribution of Mg after deformation by scanning
transmission electron microscopy and atom probe tomography revealed that clustering and segregations occurred during severe
deformation. Mg atoms agglomerate on grain boundaries (GBs), forming mostly nanoscaled clusters at room temperature and more uni-
form segregation along GBs at 200 °C. In any case, however, the equilibrium Al3Mg2 phase does not nucleate. Using post-deformation
annealing treatments, it was found that it can proceed only through a very specific orientation relationship with the face-centered-cubic
Al matrix. Both the contribution of dislocations and deformation-induced vacancies were considered to account for the enhanced
mobility of Mg atoms. From theoretical estimations it is, however, concluded that Mg atoms are dragged by the vacancy flux toward
GBs while dislocations should not play a significant role. These data provide new insights about mechanisms controlling dynamic pre-
cipitation and segregation during SPD of aluminum alloys. The segregation and formation of clusters that is revealed can additionally
contribute to the strengthening of these alloys, leading to a new understanding of dynamic ageing in non-age-hardenable alloys.
Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Plastic deformation; Grain boundary; Segregation; Diffusion; Precipitation

1. Introduction distributed in solid solution in the face-centered cubic

As they offer a good compromise of properties such as
formability, mechanical strength, weldability and corrosion
resistance, Al–Mg alloys with a typical Mg content varying
in the range of 1–5 at.% are widely used for commercial
application. Compared to pure aluminum, their higher
yield stress and strain hardening is due to solid solution
strengthening, i.e. Mg atoms are homogeneously
⇑ Corresponding author. Tel.: +33 2 32 95 51 42.
E-mail address: xavier.sauvage@univ-rouen.fr (X. Sauvage).
(fcc) Al phase and strongly interact with dislocations
[1–6]. These interactions reduce the dynamic recovery
process compared to pure aluminum, even at room temper-
ature. This leads to a higher strain hardening and a higher
dislocation density after deformation [7,8].
Using severe plastic deformation (SPD) techniques, it
has been shown that ultrafine-grained (UFG) structures
can be achieved in various metals and metallic alloys [9].
The grain size refinement mechanisms during SPD are con-
trolled by the generation of dislocations and dynamic
recovery processes, i.e. the way dislocations dynamically

http://dx.doi.org/10.1016/j.actamat.2014.03.033
1359-6454/Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
126 X. Sauvage et al. / Acta Materialia 72 (2014) 125–136
reorganize to initially form low-angle boundaries (disloca-
tion cell walls) and finally, for larger strains, high-angle
boundaries [9,10]. It has been experimentally observed that
a small amount of Mg may dramatically change the grain
size achievable by SPD. Indeed, the typical grain size
reported for pure Al processed by high-pressure torsion
(HPT) is 800 nm [11], going down to only 150 nm in an
Al–3% Mg alloy [12–14]. This trend has been confirmed
by a large number of experimental investigations [15–18]
and is obviously linked to the strong interactions of Mg
atoms with dislocations mentioned above. Besides, it is also
well known that Mg is prone to grain boundary (GB) seg-
regation. Both experimental evidence [19,20] and simula-
tion work [21–23] have demonstrated this tendency. In
our previous works [24,25] we have shown by atom probe
tomography (APT) analyses that the Mg distribution in a
homogenized Al–5.7 wt.% Mg alloy could be significantly
affected by the SPD at room temperature. High local Mg
concentrations were indeed observed along defects that
were attributed to “non-equilibrium” GBs, and the signifi-
cant deviation of the yield stress to the Hall–Petch law
recorded for this UFG structure was attributed to these
segregations [24]. Thus, the redistribution of alloying ele-
ments can significantly affect the strength, and understand-
ing the related mechanisms becomes an important problem
of modern materials science.
The aim of the present work is to propose a comprehen-
sive study of the redistribution of the solute element in a
similar supersaturated solid solution of Mg in Al. At first,
beyond fundamental interest, the present study is also
motivated by a better understanding and a better control
of microstructural features in UFG materials processed
by SPD. Indeed, GB segregations may, for example, signif-
icantly affect properties [25] such as strength [24,26–28] or
thermal stability [29–31], which is a key issue for numerous
possible applications of UFG materials. Second, the scien-
tific issue raised by this paper deals with the stability of
supersaturated solid solutions under plastic deformation.
It is indeed interesting to note that 5.7 wt.% Mg is much
higher than the equilibrium solubility limit of Mg in Al
at room temperature (below 1 at.% [32]). Thus, as reported
for the Al–Zn system [33], phase separation may occur dur-
ing SPD. However, Al–Mg supersaturated solid solutions
with only a few at.% Mg usually decompose very slowly
because of the high nucleation barrier of the b or b0 phases
(Al3Mg2) [34]. GP zones or metastable phases with a L10 or
L12 structure have also been reported [35–37] but are
unstable at room temperature or higher if the Mg content
of the alloy is below 9 at.%. In any case, GBs play a key
role by promoting heterogeneous precipitation [34]. Thus
specific features are expected in UFG structures obtained
by SPD where typically a large amount of GBs are created.
Therefore, a similar material (Al–5.7 wt.% Mg) was pro-
cessed by HPT at room temperature and 200 °C after solu-
tion treatment to clarify the influence of the processing
temperature. Then, the thermal stability and the redistribu-
tion of Mg atoms upon annealing of the UFG structure
resulting from SPD were also investigated. Contrary to
our previous work where the experimental approach was
mainly based on APT, here we have mostly used high-angle
annular dark-field (HAADF) scanning transmission elec-
tron microscopy (STEM) to characterize the distribution
of Mg. This technique cannot provide quantitative infor-
mation about local concentrations but, the field of view
being much larger, a much better statistic could be
obtained.
2. Experimental
The material investigated in the present study is a
hot-pressed commercial aluminum alloy containing 5.7%
Mg, 0.32% Sc and 0.4% Mn (wt.%), it will be named Al–
Mg in the following. Before grain refinement by SPD, the
material was homogenized at 380 °C for 2 h (above the sol-
ubility limit of Mg in fcc Al). After this treatment, the grain
size was 60 lm.
Discs (20 mm in diameter and 2 mm in thickness) were
machined for SPD by HPT at room temperature or at
200 °C. During processing, a constant pressure of 6 GPa
was applied and discs were deformed up to 20 revolutions.
This process being intrinsically heterogeneous (larger
deformation in the outer part of the disc), samples for
the microstructure characterization were always carefully
extracted always in the same region, i.e. at a distance of
6 mm from the center (approximately half the radius from
the center).
Details about X-ray diffraction (XRD) experiments were
described in our previous work [18]. Transmission electron
microscopy (TEM) samples were prepared by standard
electropolishing methods and then examined using a JEOL
ARM-200F probe corrected microscope operating at
200 kV. Observations were performed both in conventional
transmission with a parallel beam and in STEM with a
probe size of 0.2 nm and a convergence angle of 34 mrad.
STEM-HAADF images were recorded with a collection
angle in the range of 50–180 mrad and dark field (DF)
images with a collection angle in the range of 20–50 mrad.
Elemental mapping was performed using energy dispersive
X-ray spectroscopy (EDS) with a JED2300 detector. APT
samples were also prepared by standard electropolishing
techniques [38]. Analyses were performed in ultra-high vac-
uum conditions, using an energy-compensated atom probe
equipped with an ADLD detector [39] and a reflectron.
Samples were field-evaporated using electric pulses
(30 kHz pulse repetition rate and 20% pulse fraction). As
SPD samples are extremely sensitive and prone to early
specimen failure during analysis, it was impossible to ana-
lyze them at a temperature below 80 K. However, at a tem-
perature higher than 40 K, a significant amount of Mg
might be evaporated between pulses (preferential evapora-
tion), leading to non-quantitative measurements. Thus,
samples were analyzed at 80 K to avoid specimen failure
but a systematic correction was applied on the Mg content
to account for the preferential evaporation. This correction
 X. Sauvage et al. / Acta Materialia 72 (2014) 125–136 127

is based on a calibration measurement that was performed

on the non-deformed material that was analyzed by APT
both at 80 K and at 40 K (7.0 ± 0.2 at.% Mg measured at
40 K vs. 4.4 ± 0.2 at.% at 80 K).

3. Results

3.1. Redistribution of Mg atoms during SPD

As already reported in our previous work [24,25], the

homogenization treatment performed before HPT (2 h,
380 °C), leads to a very homogeneous distribution of Mg
atoms within the fcc Al matrix. The average concentration
measured by APT was 7.0 ± 0.2 at.%, i.e. very close to
the nominal composition and consistent with the fcc Al lat-
tice parameter estimated from XRD measurements
(Table 1). Besides, since the alloy contains some Sc and
Mn, it was not surprising to find some Al3Sc nanoscaled
particles with a size in the range of 5–10 nm and also signif-
icantly larger Al–Mn intermetallic particles. During HPT
at room temperature, significant modification of this origi-
nal microstructure occurred. STEM observations were car-
ried out using two detectors: (i) a DF detector that
provides images with diffraction contrast to visualize GBs
and (ii) a HAADF detector that provides Z contrast to
exhibit local composition changes (Sc- and Mn-rich clus-
ters are brightly imaged and Mg-rich clusters appear dark).
As shown in the STEM-DF image (Fig. 1b), after HPT at
room temperature, the grain size is in the range of 100–
200 nm (consistent with previous data [24,25]). Mn- and
Sc-rich precipitates also clearly appear in the STEM-
HAADF image (bright in Fig. 1a), but their size, shape
and distribution were not significantly affected by the
deformation. Besides, a large number density of nano-
scaled dark areas with various shapes (spherical, ellipsoid, Fig. 1. STEM images of the AlMg alloy severely deformed at room
plates) is exhibited in the same image. Due to their dark temperature. (a) HAADF image (Z contrast) showing bright Al3Sc
contrast, they are believed to be Mg-rich clusters or segre- spherical nanoparticles and dark zones that could be attributed to Mg-rich
clusters. (b) Dark field image where grain boundaries are clearly exhibited
gations. Their typical size or thickness is in the range of 5–
thanks to diffraction contrast.
20 nm. Many of them seem located in the vicinity or along
GBs, but others could be observed at triple junctions or
inside grains. To confirm that these dark clusters are Mg- Fig. 3a clearly shows indeed that the Mg distribution after
rich, EDS mapping was performed at a higher magnifica- HPT at room temperature is not homogeneous. The local
tion (Fig. 2b). The line scan (Fig. 2c) performed along fluctuations of the Mg concentration were quantified on
the arrow plotted in Fig. 2a confirms that bright (respec- a two-dimensional (2-D) mapping (Fig. 3b), where it is also
tively dark) particles are Sc- (respectively Mg-) rich. demonstrated that nanoscaled clusters with a size in the
Besides, spot analyses revealed local concentrations in a range of 5–10 nm and with a local composition ranging
typical range of 10–20 at.% in these dark areas against only from 10 to 20 at.% could be detected. Additionally, con-
few at.% nearby. Such nanoscaled Mg-rich clusters were ventional TEM observations were carried out and it is
also revealed by APT. The analyzed volume displayed in important to note that only Al3Sc and Al–Mn intermetallic

Table 1
Mg concentrations in the aluminum matrix in the initial material and after HPT at room temperature and at 200 °C. Data obtained by local APT
measurements are compared to estimations based on the measurement of the fcc Al lattice parameter (XRD).
at.% Mg in sol sol Initial material HPT at room temperature HPT at 200 °C
APT 7.0 ± 0.2 6.4 ± 0.5 6.1 ± 0.5
XRD 7.0 ± 0.15 6.4 ± 0.3 6.0 ± 0.1
128 X. Sauvage et al. / Acta Materialia 72 (2014) 125–136
Fig. 2. Al3Sc spherical nanoscaled precipitate and Mg-rich zones in the
AlMg alloy severely deformed at room temperature: (a) STEM-HAADF
image, (b) corresponding EDS map (Al–K blue, Sc–K green and Mg–K
red); (c) line profile along the direction indicated by the arrow in (a),
clearly indicating that bright zones in HAADF images are Sc-rich
precipitates while dark zones are Al-poor and Mg-rich. (For interpretation
of the references to color in this figure legend, the reader is referred to the
web version of this article.)
Fig. 3. APT data collected in the AlMg alloy severely deformed at 200 °C:
(a) 3-D reconstruction showing nanoscaled Mg-rich clusters (Mg atoms
are plotted in red and Al atoms in blue); (b) 2-D Mg chemical map
computed across these clusters showing that their Mg content is 10 at.%
and locally up to 20 at.% (sampling volume 2  2  2 nm3). (For
interpretation of the references to color in this figure legend, the reader
is referred to the web version of this article.)
particles gave rise to diffraction contrast in bright field, or
lattice contrast in high resolution. Besides, it was impossi-
ble to detect in diffraction patterns any reflection
corresponding to the b or b0 phases (Al3Mg2) or any other
Mg-rich metastable phases reported in the literature
[40,41].
After HPT at 200 °C, the average grain size is in the
range of 200–350 nm (Fig. 4b), significantly larger than
after room temperature processing. Mg-rich layers cover
GBs (darkly imaged on HAADF images), or are located
at triple junctions (Fig. 4a). However, a significant fraction
(in the range of 30–50%) of GBs is not covered by such seg-
regations. As reported in the literature, this could be
related to various GBs structures or misorientations [42–
44,20,19,21,22]. Few Mg-rich clusters or segregations were
also observed along some interfaces between the fcc Al
matrix and Al–Mn intermetallic particles. Beside, like in
the material processed at room temperature, it was impos-
sible to reveal b or b0 phases (Al3Mg2) or any other Mg-rich
metastable phases using diffraction in conventional TEM.
EDS analyses (Fig. 5) was carried out and it was found that
the Mg concentration along GBs and at triple junctions is
typically in the range of 10–15 at.%. This is slightly lower
than the values reported for the material processed at room
temperature. The typical width of these segregations along
 X. Sauvage et al. / Acta Materialia 72 (2014) 125–136
Fig. 4. STEM images of the AlMg alloy severely deformed at 200 °C: (a)
HAADF image (Z contrast) showing bright Al3Sc and Al6Mn particles
and few dark zones, especially along triple junctions and GBs that could
be attributed to Mg segregations; (b) dark-field image where grain
boundaries are clearly exhibited thanks to diffraction contrast.
GBs is 10 nm but there is a large scatter (Fig. 5). To con-
firm these observations, the material was analyzed by APT.
The three-dimensional (3-D) reconstruction of an analyzed
volume containing a triple junction is shown in Fig. 6
where GBs are arrowed. The grain located in the bottom
of the volume was orientated with a h1 1 1i direction close
to the analysis direction so that (1 1 1) fcc Al planes are
clearly exhibited (Fig. 6a). In this volume, the Mg distribu-
tion looks fairly homogeneous (Fig. 6b), but concentration
profiles computed across two GBs show that some small
local fluctuations may arise. One of the grain boundaries
is slightly depleted (Fig. 6c), while the other appears locally
significantly enriched in Mg (Fig. 6d). In general, from all
the collected data, it is confirmed that the length scale of
Mg concentration fluctuations is larger compared to the
material processed at room temperature.
129
Fig. 5. Al3Sc precipitate and Mg-rich zones in the AlMg alloy severely
deformed at 200 °C: (a) STEM-HAADF image; (b) corresponding EDS
map (Al–K blue, Sc–K green and Mg–K red). (For interpretation of the
references to color in this figure legend, the reader is referred to the web
version of this article.)
Since Mg-rich clusters and segregations are formed dur-
ing SPD both at room temperature and at 200 °C, the
amount of Mg in solid solution in the matrix decreases.
Local measurements by APT and macroscopic measure-
ments by XRD measurements (based on the relationship
between the lattice constant and the Mg concentration)
confirm this point and are reported in Table 1. The
relatively large scatter of APT measurements indicates that
some significant variations were observed from one
analyzed volume to another. Anyway, from these measure-
ments and assuming that these clusters/segregations have
the same molar volume than the matrix, it is possible to
estimate the average volume fraction Fv of Mg-rich clusters
or segregations as:
F v ¼ ðX o  X m Þ=ðX c  X m Þ ð1Þ
130 X. Sauvage et al. / Acta Materialia 72 (2014) 125–136
Fig. 6. 3-D reconstruction showing a triple junction in a volume analyzed
by APT in the AlMg alloy severely deformed at 200 °C: (a) Al map where
(1 1 1)fcc Al atomic planes are clearly exhibited; (b) Mg map with arrows
corresponding to the location of concentration profiles; (c) Mg concen-
tration profile showing a Mg depletion along the first GB; (d) Mg
concentration profile showing locally strong Mg segregation along the
second GB (sampling volume thickness, 1 nm).
where Xc is the mean Mg concentration of the clusters/seg-
regations, Xm the mean Mg concentration of the matrix
and Xo the nominal Mg concentration of the alloy.
In the material processed by HPT at room temperature,
Mg-rich clusters appear rather well distributed within the
microstructure, even if many of them are located in the
vicinity of GBs. Thus, if it is assumed that these clusters
are spherical with a mean radius Rc and homogeneously
distributed, then the mean distance between these clusters
Lc can be written as:
Lc ¼ Rc ð4p=ð3F v ÞÞ1=3 ð2Þ
With Xo = 7%, Xm = 6%, Xc = 20% and Rc in the range of
5–10 nm, it leads to Lc in the range of 20–40 nm, in
relatively good agreement with our observations by
STEM-HAADF (Figs. 1 and 2).
In the material processed by HPT at 200 °C, Mg-rich
zones appear mostly located along GBs as segregations.
Then, if it assumed that grains with a mean diameter d have
boundaries covered by a homogeneous Mg-rich layer, the
thickness t of this covering layer can be written as:
t ¼ dF v =3 ð3Þ
With Xo = 7%, Xm = 6%, Xc = 15%, d = 300 nm, this leads
to a segregation layer thickness in the range of 15–22 nm
(corresponding to a fraction of covered boundaries in the
range of 70–50%), in relatively good agreement with our
observations by STEM-HAADF (Figs. 4 and 5).
3.2. Redistribution of Mg atoms during annealing of the
severely deformed alloy
For a better understanding of the formation of Mg-rich
clusters and segregations during SPD, it was decided to
compare with the nucleation and growth of the b phase
or other metastable Al–Mg intermetallic phases in the
UFG structure. This could be easily achieved by a low tem-
perature annealing, typically in the range of 100–200 °C
[34,23,45]. However, to avoid any interference between
the nucleation processes and recovery or grain growth,
the UFG structure was first stabilized in the single phase
domain, at 380 °C for 2 h. As shown in Fig. 7, such treat-
ment gives rise to a significant grain growth. However,
nanoscaled Al3Sc and Al–Mn intermetallic particles that
clearly appear in the HAADF image (Fig. 7b), obviously
pin GBs, constraining the grain size in the range of 1–
2 lm. Some grayscale fluctuations on a large length scale
(a few lm) are clearly noticeable on the HAADF image.
They are typical of sample thickness modulations and can-
not be attributed to Mg concentration fluctuations. This
point was confirmed by EDS analyses. Besides, higher
magnification images did not reveal any dark clusters, thus
it is believed that nanoscaled Mg-rich domains formed dur-
ing HPT were dissolved during annealing. These observa-
tions are consistent with the Al–Mg binary phase
diagram [32]. Indeed, at this temperature the nominal Mg
concentration (5.7 wt.%) is below the solubility limit.
Then, to trigger the nucleation of the b or b0 phases, the
material was further aged at 175 °C for 15 days. As shown
in the HAADF image (Fig. 8a), it does not lead to a signif-
icant grain growth but copious nucleation of Mg-rich pre-
cipitates occurred. Most of them are located along GBs,
 X. Sauvage et al. / Acta Materialia 72 (2014) 125–136
Fig. 7. AlMg alloy severely deformed at room temperature and subse-
quently annealed for 2 h at 380 °C: (a) low magnification bright field
STEM image showing grain boundaries; (b) corresponding HAADF
image showing particles in bright (Al3Sc and Al6Mn) – no Mg-rich clusters
or segregations can be identified.
but also along Al/Al6Mn interfaces and occasionally inside
grains. It is interesting to note that few GBs are not
covered by these precipitates, and that there is a large dis-
persion of the layer covering GBs (from 10 to 100 nm). The
Mg concentration in these precipitates was measured using
EDS analyses (Fig. 8b) and was found to lie in the range of
35–40 at.%, close to the value expected for the b or b0
phases (Al3Mg2). Besides, the amount of Mg in the sur-
rounding matrix was measured in the range of 1–2 at.%,
corresponding to a volume fraction of b phase in the range
of 10–15% (estimated from Eq. (1)). High resolution TEM
(Fig. 8c) and selected area electron diffraction (Fig. 8d)
were carried out to check the crystallographic structure
of these precipitates and to determine their orientation
relationship (OR) with the matrix. The metastable hexago-
nal b0 phase was clearly identified and the OR with the fcc
Al matrix is:
131
Fig. 8. AlMg alloy severely deformed at room temperature, subsequently
annealed for 2 h at 380 °C, water-quenched and further annealed at 175 °C
for 15 days: (a) STEM-HAADF image showing extensive b’ phase
precipitation along GBs; (b) EDS map (Al blue, Mg red and Mn green)
showing an Al6Mn precipitate at a triple junction and b’ phase that has
nucleated along GBs; (c) HRTEM image showing the interface between
the fcc Al matrix and b’ phase; (d) corresponding SAED pattern where
typical reflexions of the b’ and fcc Al phases are indexed, showing their
orientation relationship. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
ð1 1 1Þb0 ==ð0 0 2ÞAl and ½1 3 1b0 ==½1 1 1Al
Probably only nuclei exhibiting such a specific OR may
overcome the nucleation barrier and grow. Thus GBs free
of precipitates are probably locations where this OR is
difficult or impossible to match.
4. Discussion
4.1. Specificities of the decomposition of the supersaturated
solid solution during HPT
Obviously, Mg-rich clusters and segregations formed
during SPD are very different in nature compared to the
b0 precipitates that nucleate during the thermal annealing
treatment at 175 °C. It is difficult to compare volume
fractions and sizes of precipitates or clusters because these
features are typically time-dependent in any precipitation
process. However, Mg-rich clusters in the material
processed by HPT at room temperature: (i) are more
homogeneously distributed (not only along GBs); (ii) do
not exhibit a crystallographic structure different from the
fcc Al matrix with a specific OR; and (iii) exhibit a large
132 X. Sauvage et al. / Acta Materialia 72 (2014) 125–136
scatter in Al/Mg ratio with local Mg concentrations much
lower than the b0 phase. Besides, Mg-rich layers along GBs
in the material processed by HPT at 200 °C: (i0 ) are signif-
icantly thicker than the GB segregations observed in the
material annealed at 380 °C; (ii0 ) are much more numerous;
(iii0 ) exhibit a higher Mg content (for some of them,
locally); and (iv0 ) do not exhibit a crystallographic structure
different from the fcc Al matrix with a specific OR.
All these differences clearly indicate that the mechanisms
leading to the decomposition of the supersaturated solid
solution during SPD are different from those operating
during a conventional thermally activated process. To
check that these observed phenomena are not specific to
the Al–Mg commercial alloy of the present study, a model
alloy containing only 2 at.% Mg was solutionized and pro-
cessed by HPT at room temperature in exactly the same
conditions. As expected, due to the lower Mg content,
Fig. 9. Al–2 Mg alloy homogenized and severely deformed at room
temperature: (a) STEM HAADF image showing Mg-rich clusters (darkly
imaged); (b) corresponding STEM dark-field image where diffraction
contrast reveals grains boundaries.
the typical grain size exhibited in STEM-BF images
(Fig. 9b) is significantly larger than in the Al–Mg alloy
(Fig. 1b); it is typically in the range of 150–300 nm. But
it is very interesting to note that Mg-rich clusters (darkly
imaged in Fig. 9a) were also formed during SPD in the
vicinity of GBs. Thus, even with a much lower driving force
for the decomposition of the supersaturated solid solution
(because of the lower Mg concentration), these atoms dif-
fuse and agglomerate during SPD.
4.2. Mg enhanced diffusion during SPD
The decomposition of the Al–Mg supersaturated solid
solution, even if it is only partial, requires a significant
mobility of Mg atoms. From the STEM-HAADF images
(Figs. 1a and 4a) it seems realistic to assume that in average
Mg atoms have to diffuse over a typical distance of about
k  d/4 where d is the mean grain size. Within the random
walk theory of diffusion, the effective diffusion distance can
be written as [46]:
keff ¼ ð6DtÞ1=2 ð4Þ
where D is the diffusion coefficient and t the time. If one
writes k = keff in Eq. (4), then it is possible to estimate
the equivalent diffusion coefficient Deq during the SPD pro-
cess. For HPT at 200 °C where the grain size d is 300 nm
and the total deformation time t = 1200 s, then it yields Deq
19
200°C  8  10 m2 s1. This is fully consistent with the
typical diffusion coefficient of Mg in fcc Al at 200 °C
reported in the literature [47]. However, for HPT at room
temperature where the grain size d is 150 nm, it yields
Deq RT  2  1019 m2 s1. Such a value of the thermal dif-
fusion coefficient of Mg in Al is typically reached for a tem-
perature of 180 °C [47].
Even if a significant part of the work required for the
HPT process is dissipated into heat by the plastic deforma-
tion of the material, it was shown both experimentally and
numerically that the temperature increase is very limited
due to the high thermal conductivity of anvils [48]. Thus,
even for a large number of revolutions, the temperature
increase of aluminum processed at a speed of 1 rev min–1
should not exceed 20 °C (i.e. from room temperature to
40 °C) [48]. Such a small change in temperature can obvi-
ously not account for the enhanced atomic mobility of Mg
atoms. However, as demonstrated in earlier works, a large
density of vacancies is often created in metallic alloys pro-
cessed by SPD at low homologous temperature, with con-
centrations up to CSPD  105 [49–55]. Since Mg atoms are
substitutional atoms in the fcc Al matrix, these SPD-
induced vacancies could significantly affect the atomic
mobility, and the diffusion coefficient should rather be
written as:
D ¼ ðC 0 þ C SPD ÞD=C 0 ð5Þ
where C0 is the equilibrium vacancy concentration and D
the diffusion coefficient of Mg in fcc Al. From Ref. [56],
the vacancy concentration in fcc Al can be written as
 X. Sauvage et al. / Acta Materialia 72 (2014) 125–136
C 0 ¼ 11:47 expðEf =k B T Þ
where Ef is the formation enthalpy of vacancies in
aluminum (0.66 eV), kB the Boltzmann’s constant and T
the temperature. From Ref. [47], the diffusion coefficient
of Mg in fcc Al can be written as
D ¼ D0 expðQ=RT Þ
where D0 = 1.49  105 m2 s1, Q = 120.5 kJ mol1,
1 1
R = 8.314 J mol K and T is the temperature. Both D
and D* are plotted in Fig. 10 and compared with the equiv-
alent diffusion coefficient estimated from Eq. (4). At low
temperature, the equilibrium vacancy concentration is
extremely low (typically 1011); thus the diffusion coeffi-
cient is dramatically affected by SPD-induced extra vacan-
cies while at higher temperatures D* converges toward the
conventional diffusion coefficient. Anyway, it is interesting
to note that both Deq RT and Deq 200°C are rather close to D*
estimated from Eq. (5), confirming that SPD-induced
vacancies could play a significant role in the Mg atoms’
mobility.
Dislocations that are continuously nucleated and that
propagate during deformation are another media that
could promote solute drag [57,58]. The critical velocity V,
above which moving dislocations do not drag Mg atoms,
can be estimated as follows [57,58]:
V ¼ ð3 þ 220:5 ÞAD=ð2b2 k B T Þ ð6Þ
where b the Burgers vector (b  2  1010 m), A the elastic
energy interaction that can be written as 3lbXe/p, with l
the shear modulus of fcc Al (l  27 GPa), X the atomic
volume in the fcc Al X  1.6  1029 m3), e the misfit (an
estimation based on the lattice expansion resulting from
Mg in solid solution leads to e  10%). This critical dislo-
cation velocity is plotted as a function of the temperature
in Fig. 11, taking both D and D* estimated from Eq. (5)
to visualize the influence of the enhanced atomic mobility
induced by SPD. If the mean dislocation velocity is well
above the curve, then it means that dislocations cannot effi-
ciently drag Mg atoms. The HPT process, both at RT and
200 °C, was performed with a rotation speed of 1 rpm,
leading to a strain rate in shear dc/dt that can be written as:
Fig. 10. Diffusion coefficient D of Mg in Al plotted as a function of
temperature (from Ref. [63]) and diffusion coefficient D* estimated from
Eq. (6), taking into account the contribution of SPD-induced vacancies.
Deq RT and Deq 200°C are the equivalent diffusion coefficients during SPD
estimated from Eq. (5) and experimental data.
133
Fig. 11. Critical dislocation velocity V for Mg solute drag as a function of
the temperature, estimated from Refs. [73]; see text for details. The critical
dislocation density V* is shifted to the left when the SPD enhanced
diffusion coefficient is taken into account. The vertical dashed lines
correspond to the two different processing temperatures (RT and 200 °C).
The horizontal dashed line at 104 m s–1 is an estimated lower bond of the
mean dislocation velocity during HPT (see text for details), showing that
solute drag was negligible during the process.
dc=dt ¼ ð2pr=60hÞ ð7Þ
where r is the distance from the disc center (r  5 mm) and
h is the sample thickness under loading (h  1 mm). Then,
using Orowan’s equation one may estimate the mean
dislocation density Vm:
dc=dt ¼ /bqV m ð8Þ
where / is the Schmid factor (to get a lower bound of Vm, it
is assumed to be equal to 0.5) and q the density of mobile
dislocations. The typical dislocation density reported for
SPD metallic alloys is usually in the range of 1012–
1014 m2; using this later value to estimate a lower bound
of the dislocation mean velocity during HPT leads to
Vm > 104 m s–1. As shown in Fig. 11, both at room tem-
perature and at 200 °C, the critical dislocation velocity
for Mg drag lies well below this lower bond value, even if
the enhanced diffusion estimated by Eq. (5) is taken into
account (V*). Thus, one may conclude that the Mg
enhanced atomic mobility during HPT at room tempera-
ture is predominantly mediated by SPD-induced vacancies,
while at 200 °C little effect, if any, of these extra vacancies
and of dislocations is expected.
4.3. Mg clustering against nucleation of b phase
In both cases, during SPD at room temperature or at
200 °C, it seems clear that the atomic mobility of Mg is suf-
ficiently high to promote clustering, segregation or precip-
itation of Al–Mg intermetallic phases. In some equilibrium
conditions, this latter situation should be expected because
at these two temperatures, the Mg concentration in solid
solution is significantly higher than the solubility limit
[32]. However, experimental data (TEM, HAADF, STEM
and APT) did not reveal such phases directly in the as-
deformed alloy, but only after a post-deformation aging
at 175 °C (Fig. 8). Nevertheless, it is well known that the
nucleation barrier of the Al3Mg2 phase is rather high and
134 X. Sauvage et al. / Acta Materialia 72 (2014) 125–136
that is why it usually nucleates almost exclusively along
GBs or along Al6Mn precipitates [34,45,59]. Thus, it could
be that the deformation time of only 20 min was not long
enough to overcome massively the nucleation barrier neces-
sary for a structural transformation. Besides, as shown in
the material aged for 15 days at 175 °C, a special OR
between the Al3Mg2 precipitates and the fcc Al matrix is
required at GBs for nucleation and growth. During SPD,
some dislocations are continuously generated and most of
them dynamically recover at the newly formed GBs, lead-
ing to a progressively change in their misorientation
through grain rotation [60]. In such a situation, if not
impossible, it is probably very unlikely that a steady state
could be reached and that some GBs could allow the nucle-
ation and growth of the Al3Mg2 with the required OR.
Moreover, it has been demonstrated that the Al3Mg2 phase
could be quite easily decomposed by SPD, both during ball
milling [61,62] or in shear bands [63]. Then, Mg-rich clus-
ters or segregations observed in the SPD processed Al–
Mg alloy could be also intermetallic particles that have
nucleated along GBs in the early stage of deformation
and later sheared and subsequently decomposed during
the HPT process. One should note that similar deforma-
tion-driven cyclic phenomena of nucleation and decompo-
sition have been reported for various metallic systems
processed by ball milling [64].
4.4. The role of SPD induced vacancies on Mg clustering and
segregations
It is, however, interesting to note that in any case,
Mg-rich clusters and/or segregations have been observed
mainly along boundaries or in their vicinities. It seems
therefore that there is a non-isotropic flux of Mg atoms
and that these solute atoms are dragged toward GBs in
the course of SPD. During deformation of fcc aluminum,
a large number of dislocations is created and their motion
is the medium for plastic deformation. Most of them are
absorbed along boundaries where they dynamically
recover, so there is a constant flow of dislocations toward
GBs. In principle, these dislocations may drag Mg atoms
[5,57,58]; however, as demonstrated earlier, the strain rate
during HPT is obviously too high and most of the disloca-
tions (if not all) move free of solute atmospheres. On the
other hand, the large density of vacancies created during
SPD [49–55] may affect also the distribution of solute
atoms. Like in irradiated materials, GBs are sinks for
vacancies (even if some of them are also probably annihi-
lated along dislocations), which leads to an anisotropic
vacancy flux toward GBs. As discussed above, the diffusion
of Mg atoms is driven by a vacancy mechanism but one
should note that Mg atoms in solid solution in fcc Al are
strongly coupled to vacancies, with a positive binding
energy in the range of 0.2–0.4 eV [8,40,41]. Thus, the
atomic scale mechanism of the SPD-induced segregation
observed in the present study is probably very similar to
that of non-equilibrium segregation resulting from
Fig. 12. Schematic representation of the diffusion of Mg toward GBs
assisted by the vacancy flux (Jv). This flux of vacancies is created by the
large level of plastic deformation, while GBs act as a sink. As a result, a
vacancy gradient and thus a vacancy flux is created from the grain interior
toward GBs. Since Mg atoms exhibit a positive binding energy with
vacancies, they are strongly coupled to these defects and a collective
motion of Mg atoms occurs. At the end, when vacancies recombine and
annihilate at the GBs, Mg atoms are left, forming clusters or segregations.
irradiation [25,65]. As represented in Fig. 12, Mg atoms
being strongly coupled to vacancies, the flux of vacancies
toward GBs drags Mg atoms during the plastic deforma-
tion, leading to strong local enrichments. Using high preci-
sion dilatometry measurements, Würschum et al. have
recently estimated that the typical free volumes in metals
processed by SPD are 103 [66]. If it is assumed that these
free volumes are exclusively created by the agglomeration
of vacancies coming from the grain interiors and if each
of those vacancies successfully drags one Mg atom, then
a fraction of 103 Mg (0.1 at.%) could be extracted from
the matrix. Our measurements show that it is in fact 5 or
10 times higher (see Table 1) but this difference can obvi-
ously be explained by the massive recombination and anni-
hilation of point defects at GBs. However, if we still
assume that each vacancy diffusing to a GB manages to
drag one Mg atom, it yields that at least about Nv = 102
vacancies were created during the HPT process (leading
to a decrease of the mean Mg concentration in the matrix
of 1 at.%). The SPD vacancy production rate Vp being
the number of vacancies created per second, it can be writ-
ten as:
V p ¼ N v =t ð9Þ
where t is the duration of the HPT process (t = 1200 s),
leading to Vp  105 s1. This estimate is consistent with
previous estimations performed from SPD-induced
chemical mixing in the Cu–Fe system deformed in similar
conditions by HPT [67].
Recently, using Small angle X-ray scattering measure-
ments, it has been shown that quenched vacancies in pure
aluminium form nanoscaled voids with a typical radius of
2 nm upon low temperature annealing (60–90 °C)
[68,69]. It is interesting to note that this size is consistent
with the size of the Mg clusters found in the present Al–
Mg alloy processed by SPD at room temperature
(Fig. 2a). This may indicate that these Mg-rich clusters
could be directly linked to the agglomeration of vacancies.
 X. Sauvage et al. / Acta Materialia 72 (2014) 125–136
Besides, the same authors have also shown that vacancy
voids in pure Al dissolve at a temperature higher than
145 °C [69]. This feature could explain why the Mg
distribution in the material processed by SPD at 200 °C
is significantly different with mostly grain boundary segre-
gations (Fig. 4a). Moreover, it is well known also that in a
temperature range of 80–120 °C, vacancies can free them-
selves from traps [41], leaving more freedom to Mg atoms
that could reorganize in the vicinity of the GBs. Of course,
dislocations and dislocation debris stored along boundaries
should play an important role in stabilizing locally Mg
atoms. Indeed, as reported for aged dilute Al–Mg alloys,
magnesium could easily segregate along dislocation loops
[8]. Besides, GBs created during SPD processes are often
called “non-equilibrium grain boundaries” because they
exhibit large local distortions (due to extrinsic dislocations)
and enhanced free volumes [9,70]. Mg atoms being larger
than Al, some elastic strain could be relaxed by Mg
segregations, giving rise to local compressive stresses and
stabilizing GBs by reducing their energy [71,72].
Summarizing the results of investigation on the alloy
subjected to SPD, it should be mentioned that the observed
phenomena may be interpreted as new mechanisms for
dynamic aging of Al–Mg alloys, making their behavior
similar to age-hardenable alloys. Indeed, the shown results
allow us to state that Al–Mg alloys deformed below 200 °C
may be hardened not only at the expense of work-harden-
ing (as a non-age-hardenable alloy) but also by forming
segregations [24] and clusters of alloying elements similar
to that on the precipitation stage in age-hardenable alloys.
The most striking difference is that the products of solid
solution decomposition in the Al–Mg alloy in the course
of SPD tend to inhibit grain boundary area. This
observation testifies that SPD may be used to produce
UFG materials of a new structural design, changing our
understanding of dynamic aging of non-hardenable alloys.
5. Conclusions
(i) The distribution of Mg atoms in solid solution in a
homogenized 1570 aluminum alloy was found to be
strongly affected by SPD.
(ii) After HPT at room temperature, Mg-rich clusters
(concentration in the range of 10–20 at.%) with a size
of 5–10 nm were observed near GBs.
(iii) If the process is carried out at 200 °C, then Mg segre-
gations (concentration in the range of 10–15 at.%)
with a thickness of 10 nm were observed along a
significant fraction of GBs and triple junctions.
(iv) These clusters and segregations do not exhibit the
composition nor the cyrstallographic structure of
the equilibrium Al3Mg2 phase.
(v) Preliminary data also show that in an alloy contain-
ing significantly less Mg in solid solution (2 at.%)
and no other elements, similar phenomenon occur.
135
(vi) It was demonstrated that the equilibrium Al3Mg2
phase typically nucleates and grows at GBs with a
very specific orientation relationship with the fcc Al
matrix. Thus it is emphasized that the continuous
evolution of GBs created during the SPD process
may not provide these conditions.
(vii) It was demonstrated that the mobility of Mg atoms is
probably enhanced by vacancies created by SPD,
while solute drag by dislocations appeared very
unlikely.
(viii) SPD-induced vacancies could annihilate at GBs,
leading to a vacancy gradient in grains and a vacancy
flux toward GBs. Since Mg atoms do exhibit a posi-
tive binding energy with these vacancies, they are
dragged by this flux toward GBs.
(ix) It may be concluded that SPD leads to new type of
dynamic aging when the Al–Mg alloy exhibits some
features of age-hardenable alloy behavior as the for-
mation of deformation-induced segregations and
clusters of alloying elements which can contribute
to the alloy’s hardening.
Acknowledgements
The authors acknowledge the financial support of the
ERA-NET.RUS Namastreco STP #122 project. Prof. D.
Embury is also gratefully acknowledged by X.S. for fruitful
discussions. R.Z., N.E. and M.M. acknowledge support by
the Russian Ministry for Education and Science through
Contract No. 14.B25.31.0017 (28 June 2013).
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