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Acta Materialia 58 (2010) 248260


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Inuence of alloy composition and heat treatment


on precipitate composition in AlZnMgCu alloys
T. Marlaud a,b, A. Deschamps a,*, F. Bley a, W. Lefebvre c, B. Baroux a
a
SIMAP, INPGrenoble-CNRS-UJF, BP 75, 38402 St. Martin dHe`res CEDEX, France
Rio Tinto Alcan Centre de Recherches de Voreppe, BP 27, 38341 Voreppe CEDEX, France
c
Groupe de Physique des Materiaux, UMR CNRS 6634, Institut des Materiaux de Rouen, Site Universitaire du Madrillet, Universite de Rouen,
76 801 Saint Etienne du Rouvray CEDEX, France
b

Received 27 May 2009; received in revised form 2 September 2009; accepted 2 September 2009
Available online 1 October 2009

Abstract
The composition of precipitates in three alloys of the AlZnMgCu system has been investigated for dierent heat treatments,
including peak-aged and over-aged states as well as near-equilibrium conditions, by combining atom probe tomography and systematic
anomalous small-angle X-ray scattering experiments. We show that the concentration of Cu in the precipitates changes during heat treatments and is alloy dependent. At low ageing temperature (120 C) the Cu content in the precipitates is close to the alloy content. The
precipitate Cu content is shown to increase with increasing temperature and Cu alloy content. We show that in near-equilibrium conditions the precipitate compositions are 33 at.% in Mg, about 15 at.% in Al, about 13 at.% in Cu and balance Zn. Our results strongly
suggest that the gradual incorporation of Cu in the precipitates during the heat treatment is essentially related to the slower diusivity of
this element in aluminium.
2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Aluminium alloys; Small angle X-ray scattering; Three-dimensional atom probe, Phase transformation kinetics

1. Introduction
Evaluating the composition of nanoscale precipitates in
multi-constituent alloys, and in particular Al alloys, has been
the subject of much research eort in the past decade [110].
In fact, the question of the composition of nanoscale precipitates in multi-constituent alloys raises many dicult questions. Firstly, the composition of non-stoichiometric
phases that show some substitution of chemical species
results simultaneously from thermodynamic volume properties (chemical driving force for precipitation, elastic strain),
thermodynamic capillarity properties (interfacial energy),
and the kinetics of the system (activation barrier for nucleation, diusion of the dierent species). Thus the composi-

Corresponding author. Fax: +33 4 76 82 66 44.


E-mail address: alexis.deschamps@grenoble-inp.fr (A. Deschamps).

tion of precipitates is certainly not determined a priori, and


depends on the thermal path followed by the material. Secondly, it is often dicult to predict the thermodynamic properties of metastable phases, and substitution of various
solute species within them.
Copper containing 7000 series Al alloys (based on the
system AlZnMgCu) are widely used for aeronautical
applications, especially in aeroplane wing structures. Over
the years, new alloys have been developed with increasing
total solute content and varying ratios between the three
main alloying elements (Zn, Mg and Cu), in order to reach
very high levels of strength [11]. However these alloys are
known to be highly susceptible to various types of corrosion (stress corrosion cracking, intergranular corrosion,
exfoliating corrosion) [1214]. Thus they often need to be
used in an over-aged state for better corrosion resistance
at the cost of a somewhat lower strength (e.g. T7651
temper as compared to T651 peak-aged temper). Due to

1359-6454/$36.00 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2009.09.003

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

the opposite eects of Zn and Cu on the electrochemical


properties of Al [15], it has been proposed that the change
in corrosion behaviour of 7000 series during over ageing is
related to changes in precipitate composition, and particularly to a Cu enrichment of the precipitates [16].
These alloys form precipitates following the classical
sequence leading from the solid solution to solution to GuinierPreston (GP) zones (at room temperature up to
120 C approximately), followed by the metastable precipitate g0 and by the equilibrium phase g [17]. More complicated sequences including vacancy rich clusters and several
types of GP zones have been identied [18,19,20], but are
mostly important in alloys where little room temperature
ageing is given before the articial ageing begins. The equilibrium phase g has the hexagonal structure MgZn2, however, it has been widely shown that some substitution of Cu
and Al occurs at small sizes [4,21,22], and the chemical
composition Mg(Zn,Al,Cu)2 has been proposed in Cu containing 7000 series Al alloys [23]. The composition of the g0
phase and the GP zones is the subject of some controversy
[4,5,24,25]. The available data leads to the conclusion that
they both contain some Al atoms, and that the Zn/Mg
ratio is <2 [4,5]. Even though a number of papers have
investigated the composition of precipitates in various
7000 series Al alloys, no systematic study of precipitate
composition as a function of alloy composition and ageing
treatment is available.
In this paper, we present a study of precipitate composition in three dierent alloys from the 7000 series family, of
dierent solute contents, followed during their heat treatment. In order to carry out such a study, it is necessary to
use an experimental technique able to characterize the composition of precipitates quantitatively, with a high relative
precision in order to distinguish between metallurgical
states whose compositions are relatively close, and able to
measure continuously the processes ongoing during the heat
treatment. Anomalous X-ray small-angle scattering
(ASAXS) consists of recording the X-ray intensity originating from the scattering by the precipitates of a transmitted
beam. This scattered intensity varies with the energy of
X-rays close to the absorption edges of the chemical species
of interest [2,26]. It is a technique particularly well-suited
for our purpose, since it is possible to carry out a timeresolved study during a heat treatment [27]. It requires,
however, that the time for X-ray energy changes and scattering measurements is small compared to the evolution
of the microstructure, so that the sample can be recorded
in the same microstructure for the dierent values of the
beam energy. In the case of 7000 series Al alloys, out of
the four main alloying elements (Al, Mg, Cu and Zn), only
two, namely Cu and Zn, can be used for an anomalous scattering study, as these have K-edge energies in the right range
for synchrotron X-ray measurements (89 keV).
As will be presented below, the ASAXS data can give
quantitative information only if it is complemented by
another experimental technique. Thus we have carried
out atom probe tomography (APT) measurements on

249

selected metallurgical states, to provide some of the missing


information. In addition some transmission electron
microscopy (TEM) and dierential scanning calorimetry
(DSC) measurements have been performed to obtain a
more basic characterization of the three alloys studied.
Finally, we have estimated the equilibrium composition
of the g phase in the three alloys investigated. This
required obtaining very large precipitates at moderate
temperatures, so that the thermodynamic conditions would
not be too far from that of the classical heat treatments.
We achieved this by heat treatments favouring precipitation at the sample surface, resulting in precipitates reaching
more than 10 lm in size. The composition of these
precipitates was then measured straightforwardly by electron-dispersive spectroscopy (EDS) in a scanning electron
microscope (SEM).
2. Materials and methods
The composition of the three alloys is given in Table 1.
The rst alloy, AA7150 (hereafter 7150), has the lowest Zn
content and the highest Cu content. The third, called PA
alloy, is under development at Rio Tinto Alcan, and has
the highest Zn content and the lowest Cu content. In addition it has the highest total solute content. The second
alloy, AA7449 (hereafter 7449) has an intermediate composition. The Mg content is similar in all three alloys. The PA
alloy includes some Sc in addition to Zr to retain more eciently the brous grain structure from rolling; however,
the Sc and Zr atoms are included in dispersoids and should
not play any signicant role in the precipitation process of
the major alloying additions. The three materials have been
processed in a similar way, ending as a rolled plate of about
25 mm thickness, with a brous grain structure. It is worth
mentioning that for these three alloys, the higher the total
solute content, the higher the strength [28].
The heat treatments leading to the usual T651 and
T7651 tempers (respectively peak-aged and over-aged
states) of the three alloys are all dierent, which makes it
dicult to obtain a meaningful comparison between the
precipitate compositions. Therefore, we have carried out
a common heat treatment on all three alloys, which is similar to industrial practice. It consists of a solution heat
treatment of 6 h at 470 C, followed by a cold water quench
(samples of 24 mm thickness), a room temperature ageing
of 4 days, a rst step ageing of 22 h at 120 C and a second
step ageing at 150 or 160 C (enabling the inuence of ageing temperature on precipitate composition to be studied).
The ramp speed to 120 C was 30 C h1 and the ramp
from 120 C to 150 or 160 C was 15 C h1. The experiments at 160 C were carried out in situ under the X-ray
beam, whereas for the 150 C ageing, samples experiencing
dierent ageing conditions were measured individually. In
the following, the materials aged 8 h at the second step of
150 C, which show the highest strength for all three materials, were named peak-aged, and the materials aged 37 h
at the second step of 150 C, which show approximately the

250

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

Table 1
Composition of the alloys (all in wt.%, Al content from balance to 100%; values in brackets are in at.%).

7150 (nominal)
7449 (nominal)
PA (measured)

Zn

Cu

Mg

Fe

Si

Zr + Ti

Sc

6.4 (2.8)
8.5 (3.6)
10.3 (4.6)

2.2 (1)
1.9 (0.8)
1.6 (0.7)

2.3 (2.7)
2.2 (2.6)
2 (2.4)

0.08
0.08
0.04

0.06
0.06
0.04

0.12
0.13
0.14

0.07

same strength, lower than that of the peak-aged state, were


named over-aged.
In addition, some samples have been measured during the
heat treatments leading to the T651 and T7651 tempers. For
the 7150 alloy, the T651 heat treatment consists of a solution
treatment, a water-spray quench, a 2% stretch, room temperature ageing, followed by a two-step ageing treatment with
soaks at 120 C and 156 C. For the 7449 alloy, the T651 heat
treatment consists of a solution treatment, a water-spray
quench, a 2% stretch, room temperature ageing, and a single
step ageing treatment at 120 C. For the PA alloy, the T651
heat treatment consists of a solution treatment, a water
aspersion quench, a 2% strain, room temperature ageing,
6 h at 120 C, and 12 h at 135 C. The T7651 temper of the
PA alloy has the same heat treatment as the T651 except
the second step duration, which is 96 h.
ASAXS measurements were carried out at the European
Synchrotron Radiation Facility (ESRF) in Grenoble,
France, on the BM02-D2AM beamline. The beam size at
the sample location was approximately 200 lm in diameter.
The intensity of the incoming beam was continuously monitored with high precision. Five values of X-ray energy were
used for the Zn edge (9477, 9557, 9607, 9632, 9652 eV) and
ve values for the Cu edge (8800, 8929, 8954, 8969,
8974 eV). Throughout all the experiments it was checked
that the X-ray energy did not change by more than 1 eV.
The relative wavelength dispersion was about 2  104.
For the time-resolved experiments, the three alloys were
placed together in the same furnace, so as to ensure that they
were subjected to exactly the same heat treatment and they
were measured under exactly the same conditions. The
anomalous scattering protocol used was the following:
For a given value of the X-ray energy the three materials
were measured one after the other; then the energy was
moved to the next value. This sequence was repeated for
three energy values close to the Zn edge and three values
close to the Cu edge. The total measurement time for this
sequence was about 5 min, during which it was assumed
that the microstructure evolution was negligible.
Then the same measurement sequence was carried out
on three reference samples, all containing small precipitates, and outside the furnace: one binary Al-Cu alloy,
one binary Al-Zn alloy, and one binary Al-Li alloy. The
two rst alloys were used to check whether any variation
in the X-ray energy occured during the numerous energy
changes during the experiments. The third alloy was used
as a reference sample (having no anomalous eect in the
energy range that was investigated), enabling a precise calibration of absolute intensity throughout the experiment.

For the ex situ measurements the same protocol was


used, except that the samples were not placed in the furnace, and ve energies per edge were measured.
For APT analyses, 0.3  0.3  20 mm3 blanks were cut
from the rolled plates and prepared into needles by standard electropolishing in 2% perchloric acid (70%) in 2-butoxyethanol at 15 V at room temperature. APT analyses
were carried out on ECOTAP and TAP atom probes, both
equipped with the same detection system [29]. Analyses
were performed at 108 Pa with a pulse fraction of 19%
and a pulse repetition rate of 2.0 kHz. The tip temperature
was set to 40 K, which does not lead to any preferential
evaporation of Mg in Al [30].
Data analyses were conducted using the software developed in the University of Rouen. Several algorithms can be
used to nd the precipitates in the recorded volumes and
their interfaces with the matrix, such as a cluster identication algorithm based on concentration thresholds [3], or a
maximum separation distance algorithm [5]. Since the heat
treatments investigated in the present work lead to the formation of well-dened precipitates, these algorithms lead
to the identication of the same objects, even though some
subtle dierences in the location of the interface can remain.
It was decided here to use the method based on concentration
thresholds. Once the interfaces of the dierent precipitates
present in the analyzed volume were identied, a dilatation
algorithm was rst applied to the detected precipitates in
order to remove the possible inuence of the precipitates
on the matrix composition (due to overlap of the evaporation trajectories). Then the matrix concentration was calculated as a function of the distance from the interface initially
detected. At a distance of about 1 nm from the initial interface, the calculated matrix concentration was found to be
independent of the distance criterion, and this value was
taken as the nal result. For the measurement of the composition of precipitates, an erosion protocol was used as suggested in Vaumousse et al. [31]. The indicated precipitate
composition that will be given is that of their cores.
Samples for TEM were prepared by ultrasonic cutting of
3 mm disks, followed by mechanical polishing to 100 lm,
and double-jet electropolishing in a solution of 1/3 nitric
acid and 2/3 methanol at 20 C, 15 V. They were
observed in a JEOL 3010 microscope operating at 300 kV.
Samples for DSC were polished to disks of 4 mm in
diameter and 0.5 mm in thickness. They were measured
in a Perkin Elmer Pyris Diamond apparatus, cooled to
135 C. They were heated at 350 C min1 up to
550 C. A pure Al sample of similar mass was placed in
the reference furnace. The signal was corrected by a baseline measurement carried out under the same conditions.

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

Samples for surface precipitation were prepared as follows: they were rst polished to 0.25 lm with a diamond
paste. They were then solution heat treated at 470 C for
1 h, followed by a controlled cooling of 10 C h1 to
350 C, and a 10 h heat treatment at this temperature
(which was chosen to promote precipitation at the grain
boundaries following the study of Godard and co-workers
[32]. The complete heat treatment was carried out under a
nitrogen atmosphere. The samples were then observed in
an SEM, using an accelerating voltage of 12 kV for the
EDS composition measurements. It was checked that
changing the acceleration voltage in this range did not
change the measured composition. In addition observations of the surface cross-sections revealed that the precipitate thickness was about 2 lm, and Monte Carlo
simulations of the electron trajectories in the SEM showed
that the travelled distance was smaller than this value. Ten
measurements were carried out for each material.
3. Qualitative comparison of the three alloys byTEM and DSC
The aim of this paper is to study the changes in precipitate
composition and related changes in the composition of solid
solution induced by modications of the alloy composition
and the heat treatment. It is thus important to ensure that
the microstructures of the three alloys studied are qualitatively similar, or in other words that the nature and the scale

251

of the precipitates present are the same. We have thus


observed the three alloys in their peak-aged state and the
7449 alloy in the over-aged state by conventional TEM.
Fig. 1ad shows the bright eld TEM micrographs of these
metallurgical states. It is apparent that the three alloys have
a very similar precipitate microstructure. The analysis of the
diraction patterns (not shown here) in the [1 1 1] matrix
zone axis using the protocol of Ref. [33] identies the phase
as predominantly g0 . The over-aged state has a larger precipitate size, and has been identied using diraction patterns as
consisting mostly of the stable g phase. The similarity of the
microstructures of the three alloys in their peak-aged condition is further assessed by a DSC scan performed at a high
heating rate (350 C min1) on these three materials
(Fig. 2). Two well-dened dissolution peaks are visible, the
rst of which corresponds to the dissolution of the g0 phase,
and the second to the dissolution of the g phase formed by
transformation from g0 to g during the heating stage (this
transformation being responsible for the interruption of
the dissolution process around 370 C). These dissolution
peaks, characteristic of the thermodynamic stability of the
precipitates present (including the capillarity eects due to
their very small size), are almost identical in the three alloys,
although it is possible to observe a slight delay in the dissolution of the 7150 alloy. This dierence can be related to the
higher Cu content of this alloy insofar as Cu has been shown
to increase the phase stability in this alloy system [34].

Fig. 1. Conventional TEM micrographs showing the precipitate microstructures in (a) peak-aged 7150 alloy; (b) peak-aged 7449 alloy; (c) peak-aged PA
alloy; (d) over-aged 7449.

252

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

Enthalpy (endothermic, W/g)

1.5

7150
7449
PA

0.5

100

200

300

400

500

Temperature ( C)
Fig. 2. DSC thermograms obtained on the three alloys initially in their
peak-aged state and heated at 350 C min1 up to 550 C.

4. Study of selected metallurgical states by APT


Similarly to TEM, four metallurgical states have been
selected for observation by APT, in order to evaluate the
concentrations of the dierent species in the precipitates
and in the matrix. In fact, the precipitate composition
has only been evaluated on a very small number of objects
(510 precipitates for each state), and therefore the values
that will be given are only intended to give trends. The
evaluation of the matrix solute content, however, is more
precise because the statistics of the number of atoms

probed is large and because we can assume that the solute


composition is relatively uniform in the material.
Fig. 3 shows four reconstructed volumes of APT for the
dierent metallurgical states. Qualitatively the microstructures correspond to that observed by TEM: the precipitate
size and morphology are similar in the three alloys at peak
strength, and the over-aged state shows much larger precipitates. It is also clearly visible that the solute content of the
matrix is much lower in the over-aged state as compared to
the peak-aged states.
More quantitatively, Fig. 4 shows the results for the analysis of the solid solution in these four materials. In the 7449
alloy, the total solute content of the matrix in the over-aged
state is much smaller as compared to the peak-aged states of
the three alloys (1.1 at.% vs. 2.6 at.%). In the three peak-aged
states the total solute content of the solid solution is approximately independent of the alloy composition. However, the
contents of the dierent species in the three alloys in their
peak-aged state are very dierent. The Cu solute content is
roughly similar in the three materials, whereas the Zn and
Mg contents are strongly alloy dependent: the PA alloy,
which has both the highest solute content and the highest
Zn content, has a very high residual Zn solute content and
a very low Mg content, whereas in the 7150 alloy, the solute
contents in both species are similar. The solute content of the
7449 alloy lies in between that of the two other alloys, corresponding to the global alloy compositions.
Table 2 gives the same information, for the precipitates.
The precipitate compositions have been measured using a
protocol described in Ref. [3], in order to suppress as much
as possible the inuence of the diuse interface between the
precipitates and the matrix, caused by the dierence in evap-

Fig. 3. Reconstructed volumes of the three alloys in peak-aged condition and 7449 alloy in over-aged condition. Only solute atoms are represented.

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

from the 7150 to the PA alloy with the 7449 in between) are
found also for the solute contents. This, together with the
matrix residual solute fractions, supports the hypothesis
of a constant Mg solute fraction:

100

Matrix composition (at%)

253

3
2.5
2
1.5
1

Al
Mg
Cu
Zn

0.5
0
7150
7449
PA
7449
Peak-aged Peak-aged Peak-aged Over-aged

Fig. 4. Matrix compositions (at.%) of the three alloys in the peak-aged


state and the 7449 alloy in the over-aged state, obtained from the APT
experiments. The standard deviation of all measurements presented here is
of the order of 0.05 at.% or less.

oration elds of the two-phases. However, due to the very


small size of the precipitates, this protocol was not sucient
to completely suppress this eect and we had to make some
assumptions in order to know how much Al had to be
removed from the measured composition. We have thus
assumed that the precipitates, whether of the g0 or the g
phase, had the general composition Mg(Al,Zn,Cu)2, and
therefore that the Mg content was 1/3. It will be shown later
in this paper that this hypothesis is valid in near-equilibrium
conditions (surface precipitation). The precipitate volume
fraction was calculated from the balance of Mg between
the matrix (the concentration of which is taken from
Fig. 4) and a precipitate composition of 1/3, assuming equal
atomic volumes in the precipitates and the matrix:
fv

Mg
X Mg
o  X ss
:
Mg
X Mg
p  X ss

This method is actually much more precise in comparison with a direct measurement from the precipitates
detected by APT because of the small number of precipitates found.
It can be noticed that the Cu and Zn contents in the precipitates evolve in an opposite directions: the trends in the
alloy composition (higher Zn content and lower Cu content

Table 2
Estimation of precipitate composition (at.%) and volume fraction (%)
based on the Atom Probe Tomography analyses, making the assumption
that the Mg content is 33 at.%.

7150 peak-aged
7449 peak-aged
PA peak-aged
7449 over-aged

Zn

Cu

Mg

Al

fv

30
42
41
45

10
7
5
10

33
33
33
33

27
18
21
12

4.8
5.7
6.3
7.1

if the Mg content is xed in the phase, it is expected that


the other species distribute consistently with the alloy
composition in the precipitates, in other words, the alloy
with the highest Zn content has the precipitates with the
highest Zn content;
when the alloy is supersaturated in (Zn + Cu), which
means that the (Zn + Cu)/Mg ratio is higher than 2 as
is the case for the PA alloy, the Mg residual matrix concentration comes close to zero, whereas in the opposite
case, as found for the 7150 alloy, the remaining Mg solute in solution is higher.
It is observed, on the other hand, that the Al content is
more variable. This is probably due to imperfections in the
measurement protocol. However, the values still correspond quite well to data previously published on similar
systems [4], with Al contents in the precipitates of the order
of 1520% for peak-aged states and 1015% for the overaged T7 sate.
Finally, the evaluation of precipitate volume fraction
gives an indication that it is highest in the material containing the highest solute content, and that it evolves signicantly from the peak-aged to the over-aged material.
5. Quantication protocol for precipitate microstructures
using ASAXS
Anomalous small-angle scattering experiments give
access independently to two main types of information:
information on the size and morphology of precipitates
as well as information on their volume fraction and their
composition (through the electron density contrast). The
rst information resides in the angular dependence of scattered intensity (or dependence on q-vector, where
q = 4p  sin h/k, where h is the half-scattering angle and k
the X-ray wavelength); and the second, in the absolute level
of the scattering. In the present study, the emphasis being
on the precipitate composition, the morphological study
will be restricted to the measurement of the so-called Guinier radius. This has been shown to represent well the average size of the precipitates in similar systems, and is
calculated using the following equation:
!
q2 R2g
:
2
I / exp 
3
It can be either measured from the slope of a ln (I) vs. q2
curve (Guinier plot) or from the q-value where the
p maximum of I  q2 vs. q (Kratky plot) is found qmax = 3/Rg.
The information on the precipitate composition and volume fraction depends on a rather simple equation that can
be written for the case of a two-phase system (using the rea-

254

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

sonable rst-order assumption that the precipitates all have


the same composition):
Z 1

2
Qo
I  q2 dq 2p2 qp  qm  fv 1  fv ;
3

20

Cu K edge

where Qo is the so-called integrated intensity, which can be


measured from the experimental data, and qm and qp are
respectively the matrix and precipitate average apparent
electronic densities. The total integrated intensity is calculated rst for the range of scattering vectors covered by
the CCD camera, and then extrapolated to innity using
Porod asymptotic behaviour [4].
If one assumes, in addition, that the average atomic volumes of the matrix and precipitates are identical (which is
here a very good approximation), the apparent contrast in
electronic density can be written as a function of the dierence in average X-ray scattering factors, which depend on
the energy used:
P
P
fi X p  i fi X mi
;
4
qp  qm i i
V at
where the sum on i is made over all atomic species, fi is the
scattering factor of atom i, and X pi (respectively X mi ) is the
atomic concentration of element i in the precipitate (respectively the matrix). The scattering factors can be written as
follows:
fi Z i fi0 i fi00 ;

where Zi is the atomic number of atom i, and f0 and f00 are


the corrective factors which depend on the X-ray energy
used. In this work we have used X-ray energies close to
the Zn and Cu edges; in this range the scattering factors
of Al and Mg can be considered as constant to a good
approximation. The variations in scattering factors of Zn
and Cu as compared to Al are given in Fig. 5. They show
that a contrast variation of about two electrons was obtained in the measured energy range for the two edges.
Fig. 6a and b illustrates the variation in scattered intensity
for the same material (7150 alloy in the peak-aged state) at
dierent energies, around the Zn and Cu edges. The contrast between the Zn (or Cu) and Al decreases when
approaching the Zn (or Cu) edge, along with the scattered
intensity if the composition in Zn (or Cu) is larger in the
precipitates in comparison to the matrix, as is the case here.
The contrast in apparent electronic density must be written in more detail to obtain a quantication of the precipitate compositions. In the quaternary system AlZnMg
Cu, probed at the Zn and Cu absorption edges, it can be
considered that fAlfMg is constant and equal to 1. Thus
Eq. (4) becomes:
V at Dq fZn  fAl  X pZn  X mZn fCu  fAl
 X pCu  X mCu  X pMg  X mMg ;

which can be written in a simpler manner:


V at Dq DfZn=Al  DX Zn DfCu=Al  DX Cu  DX Mg ;

Zn K edge

18

16

Zn/Al

f 14

f
12

Cu/Al

E-range
investigated

10

E-range
investigated

8
8800

9000

9200

9400

9600

9800

X-ray energy (eV)


Fig. 5. Variation of the X-ray diusion factor contrasts (Df) between (Zn
and Al) and (Cu and Al) a function of X-ray energy, corresponding to Eq.
(7) in the text. The energy ranges investigated during the ASAXS
experiments are indicated close to the Cu and Zn K-edges. In both cases
they give access to a contrast variation of more than two electrons for the
species considered.

where DXi is the dierence in atomic concentration of element i between the precipitates and matrix.
This electronic density contrast can be included in Eq.
(3), providing the following relationship between the integrated intensity, the volume fraction and the composition
contrast terms:
"
#
p
p
2p2 fv 1  fv
1
DX Mg
Q0
V at
DfZn=Al
p 

DfCu=Al
2p2 fV 1  fV

8
DX Zn
 DX Cu :
V at
DfZn=Al
p
The term 2p2 fv 1  fv DX Mg =V at on the left-hand side
has a maximum value (for fv = 0.1 and DXMg = 0.33) more
than one order of magnitude smaller than the square root
of the integrated intensity. Thus the above equation can be
simplied as follows:
p 
p

Q0
DfCu=Al
2p2 fV 1  fV

DX Zn
 DX Cu : 9
V at
DfZn=Al
DfZn=Al
A graph representing
the (presumably) linear relationp
ship between
Q0 =DfZn=Al and DfCu=Al =DfZn=Al provides
two sets of equations, linked to the slope A and the ordinate at the origin B, to which we can add the balance of solute species in the precipitates:
B  V at
X pZn X mZn p ;
2
2p fV 1  fV
A  V at
X pCu X mCu p ;
2p2 fV 1  fV

X
i

X pi 1:

10

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

(a)

9477
9557
9607

Fig. 7 shows one example of the plot corresponding to


Eq. (9). It is found that the experimental data is distributed
well along a straight line, which indirectly validates the
hypothesis made (as the neglected terms would give non
linear contributions to this plot). A high sensitivity of the
composition in the two species (Zn and Cu) is obtained,
and the volume fraction is also determined.

Zn edge

9632
9652

-5

I.q (A )

0.8

255

0.6

6. Evolution of precipitate compositions during a model heat


treatment on the three alloys

0.4

0.2

0
0

0.05

0.1

0.15

0.2

0.25

0.3

-1

q (A )

(b)

8800

8954
8969

8974

-5

I.q (A )

8929

0.5

Cu edge
0
0

0.05

0.1

0.15

0.2

0.25

0.3

-1

q (A )
Fig. 6. Scattering curves in a Kratky plot for the 7150 alloy in the peakaged state, as a function of the X-ray energy; (a) energies close to the Zn
edge and (b) energies close to the Cu edge. It appears that the curves are to
a very good approximation proportional to each other, which means that
the ASAXS procedure can be applied on an average measurement such as
the integrated intensity. Intensity variation with X-ray energy is clearly
observed, in a larger extent for Zn as compared to Cu.

Fig. 8ad shows the evolution of the main precipitation


parameters, Cu and Zn concentrations in the precipitates,
volume fraction, radius and number density, during the
heating ramp from 120 to 160 C and during the 160 C
heat treatment.
The evolution of the Cu concentration in the precipitates at the beginning of the experiment is striking: after
the 120 C ageing step the precipitates contain only a small
amount of Cu (02 at.%), whatever the alloy. In contrast,
they contain a high proportion of Zn. During the ramp
to 160 C and the rst few hours at 160 C, the Cu concentration in the precipitates increases rapidly reaching 610%.
The level reached is highest in the 7150 alloy, lowest in the
PA alloy, and intermediate in the 7449 alloy, which is consistent with the relative compositions in Zn and Cu of the
three alloys. This increase in Cu precipitate concentration
is accompanied by a parallel decrease in the Zn content.
The volume fractions of precipitates deduced from our
experiments show a similar trend in the three materials,
though with a large shift between them. The alloy with
the highest solute content (PA alloy) has the highest volume fraction, and so on. We observe a decrease in the volume fraction during the heating ramp, together with a large
decrease in number density (almost one order of magnitude) and a large increase in size. This is characteristic of
partial dissolution of small precipitates during heating

1/2

The matrix compositions in Zn and Cu are generally


small compared to the precipitate ones, and we can make
reasonable estimates of their values. However the two
above equations still have three unknowns, namely X pZn ,
X pCu and fv. Some additional assumptions were made, based
on the analysis of the atom probe data:
The composition in Mg has been taken as constant and
equal to 0.33; this is equivalent to stating that the g0
phase has a composition of Mg(Zn,Al,Cu)2.
The composition in Al has been taken as constant and
equal to 0.15.
Changing these two hypotheses does actually not change
signicantly the Cu fraction found inside the precipitates
(1 at.%); the variation is somewhat larger on the Zn fraction (5 at.%).

/f

Zn

at Cu edge f /f
Cu

0.028

at Zn edge f /f
Cu

Zn

Zn

= 0.613
= 1.715

0.027

close to Zn edge
0.026

X =9.9 at%
Cu

X =41.8 at%

0.025

Zn

f =4%

close to Cu edge
0.024
0. 6

0. 8

1. 2

1.4

f /f
Cu

Zn

Fig. 7. Plot of Eq. (9) in the same material as Fig. 6, whose slope and
origin provides a measurement of the precipitate composition (at.%) in Cu
and Zn.

256

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

(a)

(c)

165

Temperature
160

8
150
6

145

135

7150
7449
PA

130

0
0

10

15

20

155
0.05

145

0.04

140

0.02
0

125

135

7150
7449
PA

0.03

Ageing time (h)

10

130
125
20

15

Ageing time (h)

(b)

(d)

52

165

48

150

46

145

-3
o

140

44

135
42
130
40
0

10

15

20

125

155

Density

Radius

20

4.5
4

15

3.5

7150
7449
PA

10

3
2.5

Precipitate radius (nm)

7150
7449
PA

Precipitate number density (10 m )

160

50

5.5

25

Temperature
Temperature ( C)

Zn concentration in precipitates (at %)

150

140

160
Temperature ( C)

155

Precipitate volume fraction

10

165
Temperature

0.06
Temperature ( C)

Cu concentration in precipitates (at %)

12

2
1.5

0
0

10

Ageing time (h)

15

20

Ageing time (h)

7. Comparison with the evolution during other heat


treatments
Similar measurements have been made at a temperature
of 150 C for the second heat treatment step, with the same
initial step at 120 C. However, for practical reasons it was
only possible to carry out these experiments on ex situ samples. This results in more variability in the experimental
data, since every data point comes from a dierent sample.
However the same trends are found on all parameters of
the microstructure: evolution of volume fraction and solute
contents as shown in Fig. 10 (the evolution of size and den-

-3

Radius

5
4

slope 1/3

7150

Density

Precipitate radius (nm)

due to the increase in the local equilibrium concentration at


their interface with the matrix. In later stages of ageing a
classical LifschitzSlyozovWagner (LSW) coarsening law
with R / t1/3 and N / t1 can be observed, as shown in
Fig. 9. It is observed that the proportionality ratios of this
LSW law are dierent for the three alloys, and that coarsening is faster in the highest Zn, lowest Cu containing alloy
(see Fig. 9).

Precipitate number density (10 m )

Fig. 8. Evolution of the microstructural parameters deducted from the ASAXS measurements during the 160 C heat treatment: (a) Cu concentration in
the precipitates; (b) Zn concentration in the precipitates; (c) volume fraction; (d) precipitate size and number density. The missing data around 5 h of heat
treatment corresponds to an interruption of the synchrotron beam during the experiment.

7449
PA

slope -1

0.8

1
5

10

20

Ageing time (h)


Fig. 9. Same data as in Fig. 8d in a loglog plot showing the power law
dependence of precipitate size and density with time.

sity are also similar but have been omitted for gaining
space). The most striking dierence with the 160 C heat
treatment is that the enrichment in Cu of the precipitates

T. Marlaud et al. / Acta Materialia 58 (2010) 248260


100

155

Temperature

145

140

135

130

7150
7449
PA

2
1

125
120

0
0

10

15

20

25

30

3
2.5
2
1.5
1

Al
Mg
Cu
Zn

0.5

115

Ageing time (h)

(b) 52

7150
Peak-aged

155

7449
Peak-aged

PA
Peak-aged

Temperature
150

50

145
48

140

46

135

40

125

7150
7449
PA

42

10

15

20

25

130

44

Temperature ( C)

Zn concentration in precipitates (at%)

Matrix composition (at%)

150

Temperature ( C)

Cu concentration in precipitates (at%)

(a)

257

120
30

115

Ageing time (h)


Fig. 10. Evolution of (a) Cu and (b) Zn concentrations in the precipitates
during the 150 C heat treatment on the three alloys.

is much more limited: a 7.5% maximum for the 7150 alloy


compared to 10% at 160 C.
The peak-ageing states studied by APT in Section 4 have
been obtained at 150 C. As the most reliable information
that can be extracted from the APT data is the residual
solid solution content, it is worth comparing it with the solute contents that can be calculated using the mass balance
for each species from the ASAXS data. These compositions
are shown in Fig. 11. Although some dierences exist, all

Fig. 11. Matrix compositions for the three materials in their peak-aged
state deduced from the ASAXS measurements, using the solute balance
with the measured precipitate volume fraction and composition.

the trends found with APT are conrmed, namely that


the total solute content in the three materials is similar, that
the Cu solute concentration is relatively insensitive to the
alloy, and that the largest dierences between the alloys
are found in the Zn and Mg compositions.
It is also worth investigating if the more realistic T651
and T7651 heat treatments of these three alloys give similar
trends compared to the model heat treatments. Two additional complexities arise: rst, these heat treatments introduce a pre-deformation step after the quench following the
solution heat treatment, which changes both the nature of
precipitates present and the precipitation kinetics; second,
these heat treatments are not realized at the same temperatures for the three alloys (156 C for the 7150 alloy,
120 C for the 7449 alloy and 135 C for the PA alloy).
Fig. 12 shows TEM micrographs of the T651 tempers
for the three materials. Despite the dierences in heat treatment temperatures (that are compensated by dierent heat
treatment times), the microstructures are again very similar. Diraction patterns conrm that both g2 and g0 pre-

Fig. 12. TEM micrographs of the microstructures of the T651 states of the three materials.

258

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

Table 3
Microstructure parameters deducted from the ASAXS measurements carried out on the industrial T651 heat treated materials.
Precipitate radius (nm)

Volume fraction (%)

Zn in precipitates (at.%)

Cu in precipitates (at.%)

156 C
120 C
135

35
20
27

3.9
5.7
7.6

42
49
48

10
3
4

Cu concentration in precipitates (at%)

120

100

T7651

T651

60

1
0

80

40

20

40

60

80

100

20

Ageing time (h)

(b) 50

140

Temperature
120

49

100
48
80

47

Temperature ( C)

All the results presented above give a consistent picture


of the evolution of precipitate composition during heat
treatment, and as a function of alloy content. During the
low temperature ageing steps (120 C), the precipitates contain almost no Cu, and their Zn composition is close to
50 at.%. As the temperature of the heat treatment is raised,
or the length of the heat treatment is increased, the Cu

140

Temperature

8. Discussion

(a) 6

Temperature ( C)

cipitates are present, the former being large platelet precipitates visible edge-on, nucleated on the dislocations, and
the latter being homogeneously nucleated precipitates, similar to that observed in the model peak-aged states investigated above.
Table 3 gives the microstructure parameters evaluated
from ASAXS for the three alloys. The same trends are
again observed, namely that the PA alloy has a lower Cu
precipitate content as compared to the 7150 alloy. However, this dierence is stronger as compared to the previous
data. This is certainly due to the dierence in heat treatment temperature as we have seen above that Cu enrichment was already more limited at 150 C as compared to
160 C. Moreover, the Cu content inside the precipitates
is actually lower in the 7449 as compared to the PA alloy,
which is contrary to what is observed at the common temperature of 160 C. Again, this can be attributed to the
lower heat treatment temperature of the 7449 alloy in its
T651 temper. The precipitate radius in this peak-aged state
is also shown to be dierent in the three materials. For the
7150 and PA alloys, it is close to usual values for 7000 series alloys in their peak-aged condition, namely around
3 nm. The value for the 7449 alloy seems somewhat low,
and it is suspected that a longer ageing time may have
resulted in a slightly higher strength.
Finally, the evolution of the precipitate composition has
been evaluated during the second heat treatment step of the
PA alloy at 135 C. Fig. 13 shows the evolution of the Cu
and Zn atom fractions during this heat treatment. Again
the same trends are observed: there is an initial fraction
of about 2 at.% Cu in the precipitates, followed by a gradual enrichment in Cu accompanied by a loss of Zn during
the ageing leading to the T651 temper and later to the
T7651 temper. In the T7651 temper, the Cu content of
the precipitates, of 5 at.%, is slightly higher compared to
that of the T651 temper, showing that during the precipitate coarsening some Cu enrichment has occurred. However it stays low compared to the levels obtained at 150
and 160 C.

Zn concentration in precipitates (at%)

7150 T651
7449 T651
PA T651

Temperature of last ageing step

60

T651
46

40

T7651
45
0

20

40

60

80

100

20

Ageing time (h)

Fig. 13. Evolution of (a) Cu and (b) Zn concentrations in the precipitates


during the industrial heat treatment on the PA alloy during the 135 C
heat treatment step.

composition increases progressively up to concentrations


between 3 at.% and 10 at.% for the peak-ageing states
investigated. This value is strongly dependent on the alloy
content and the ageing temperature.
These composition variations can have both a kinetic
(dierences in diusion constants of the main alloying elements) or thermodynamic (dierences in equilibrium concentrations of the solute species) origin. In order to
estimate the equilibrium concentration of the g phase in
the three alloys, we have measured its composition on 20lm size surface precipitates (see Section 2). Fig. 14 shows
a representative micrograph of these surface phases, and
the values of the measured precipitate compositions for
the three alloys are given in Table 4. The rst remarkable

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

259

controlled. In fact, the diusion rates of the various solute


species are known to be quite dierent. At 150 C, taking
the data of Ref. [35], the diusion constants in Al (in units
of 1020 m2 s1) are approximately 4 for Zn, 3 for Mg, and
0.1 for Cu. The slower diusivity of Cu explains the progressive increase (from a value close to the average Cu solute content, namely 1 at.%) of the Cu fraction in the
precipitates towards the equilibrium value of 1314 at.%,
during the heat treatment. It also explains why the Cu content is higher when the temperature is raised, and that it is
higher in the alloy that has the highest initial Cu content,
although the equilibrium concentration is only slightly
aected. Finally, it explains why the coarsening rate constant is higher in the alloy where the Cu content of the precipitates is lowest (PA alloy).
Fig. 14. Back-scattered scanning electron microscopy image of the surface
precipitation in the 7449 alloy. The white precipitates are equilibrium g
precipitates, which are homogeneous in composition as apparent from
their homogeneous contrast. The grey phases are Al7Cu2Fe precipitates.

feature is that the Mg composition is in all cases precisely


1/3. This validates again the hypothesis made throughout
this work of a phase composition of Mg(Zn,Al,Cu)2 as a
basis for interpreting the APT and ASAXS data. Secondly,
it is apparent that even close to equilibrium, these precipitates do contain a signicant amount of Al (1015 at.%).
This amount does not seem to be strongly alloy dependent,
even though it is somewhat smaller in the PA alloy, which
has the strongest alloying content. Again, these values are
consistent with that of the atom probe results, and justify
the hypothesis of a constant Al content of 15 at.% used
for the ASAXS data interpretation. Finally, the Cu content
of these near-equilibrium precipitates is found to be 13
14 at.% in all three alloys, which is higher than all values
measured during the heat treatments leading to the peakaged or over-aged states (210 at.%). Moreover, the Cu
content of the surface precipitates is found to be only
mildly alloy dependent. As a matter of fact, the dierence
in Cu content in the macroscopic g phase for the three
alloys is much smaller than that found during the lowertemperature heat treatments.
These measurements give a strong indication that the
dierences in solute contents found between the dierent
alloys and for the heat treatments are essentially kinetically

9. Conclusions
This paper presents a systematic study of the composition of precipitates in three alloys of varying solute contents, all from the AlZnMgCu (7000 series Al alloy)
system, using a combination of experimental techniques,
and most importantly time-resolved ASAXS and APT.
The main results can be summarized as follows:
In near to equilibrium conditions, precipitates have been
found to contain precisely 33 at.% Mg, and an Al content of 1015 at.%. Their Cu content has been found
to be around 13 at.% irrespective of alloy content.
After ageing at low temperatures (120 C), the precipitates have been found to contain almost no Cu. The
Cu content of precipitates has been found to increase
progressively towards values of 310 at.% during heat
treatments at higher temperatures (in the range 135
160 C). It is higher in the highest Cu containing alloy,
and for the highest heat treatment temperatures. In no
case was the Cu content found to reach the value of
the near-equilibrium condition.
At peak-ageing, very strong dierences in residual solid
solution concentrations are found in the dierent alloys,
related to the excess alloy ratio between (Zn + Cu) and
Mg contents.
The dierences in precipitate compositions in the three
alloys and during the various heat treatments have been
shown to be consistent with a kinetic control, due to the

Table 4
Composition of the near-equilibrium surface precipitates (such as shown in Fig. 14) measured in the SEM for the three materials.
Zn

Cu

Mg

Al

Cu/Zn

7150

Solute content (at.%)


Standard deviation

38.6
1.1

13.3
0.7

33.2
1.1

14.9
0.8

0.35

7449

Solute content (at.%)


Standard deviation

38.3
1.6

13.8
0.6

33.3
1.2

14.6
0.5

0.36

PA

Solute content (at.%)


Standard deviation

42.2
1.9

12.6
2.0

33.9
0.6

11.3
0.6

0.30

260

T. Marlaud et al. / Acta Materialia 58 (2010) 248260

slower diusivity of Cu in Al compared to Mg and Zn


atoms. One consequence has been shown to be an accelerated precipitate coarsening in the lowest Cu containing alloy.
As a consequence of these ndings, the present paper
shows that the composition of precipitates (and correspondingly that of the residual solid solution) can be tuned
by adjusting the alloy composition and the heat treatment
temperature. While the amount of Al inside the precipitates
does not seem to be very sensitive to these process parameters, the substitution between Zn and Cu atoms can be at
least partly controlled. Since it is recognized that Cu and
Zn atoms have opposite eects on the electrochemical
potential of Al, it can be expected that such substitutions
impact the corrosion properties. Results regarding this
topic will be the subject of a future publication.
Acknowledgements
The sta of the D2AM/BM02 beamline of the ESRF is
gratefully acknowledged for help with the ASAXS experiments. Dr. C. Henon and Dr. C. Sigli of Alcan CRV, as
well as Dr. J. Dunlop, are thanked for fruitful discussions.
References
[1] Fuller CB, Murray JL, Seidman DN. Acta Mater 2005;53:5401.
[2] Cerezo A, Hirosawa S, Sha G, Smith GDW. In: Phoenix AZ,
Warrendale PA, editors. Proceedings of solidsolid phase transformations in inorganic materials, 2005, vol. 1. TMS; 2005. p. 251.
[3] Lefebvre W, Danoix F, Da Costa G, De Geuser F, Hallem H,
Deschamps A. Surf Interf Anal 2007;39:206.
[4] Dumont M, Lefebvre W, Doisneau Cottignies B, Deschamps A. Acta
Mater 2005;53:2881.
[5] Sha G, Cerezo A. Acta Mater 2004;52:4503.
[6] Ringer SP, Sofyan BT, Prasad KS, Quan GC. Acta Mater
2008;56:2147.
[7] Edwards GA, Stiller K, Dunlop GL, Couper MJ. Acta Mater
1998;46:3893.
[8] Murayama M, Hono K. Acta Mater 1999;47:1537.

[9] Chang CST, Wieler I, Wanderka N, Banhart J. Ultramicroscopy


2009;109:585.
[10] Marquis EA, Seidman DN, Asta M, Woodward C. Acta Mater
2006;54:119.
[11] Warner T. Mater Sci Forum 2006;519521:1271.
[12] Zhao X, Frankel GS. Corros Sci 2006;49:920.
[13] Kuntz C, Keddam M, Schuster D, Takenouti H. ABT Metall
1997;37:285.
[14] Zhao X, Frankel GS. Corros Sci 2007;49:3089.
[15] Hollingsworth EH, Hunsicker HY. Corrosion of aluminum and
aluminum alloy. In: Corrosion JR, Davis Sr, editors. Metals Handbook, 9th ed., vol. 13. Materials Park, OH: ASM International; 1987.
p. 583609.
[16] Staley JT, Byrne SC, Colvin EL, Kinnear KP. Mater Sci Forum
1996;217222:1587.
[17] Lendvai J. Mater Sci Forum 1996;217222:43.
[18] Waterloo G, Hansen V, Gjnnes J, Skjervold SR. Mater Sci Eng A
2000;303:226.
[19] Berg LK, Gjnnes J, Hansen V, Li XZ, Knutson-Wedel M, Waterloo
G, et al. Acta Mater 2001;49:3443.
[20] Li ZH, Xiong BQ, Zhang YG, Zhu BH, Wang F, Liu HW. Mater
Charact 2008;59:278.
[21] Brenner SS, Kowalik J, Hua MJ. Surf Sci 1991;246:210.
[22] Deschamps A, Bigot A, Livet F, Auger P, Brechet Y, Blavette D.
Philos Mag A 2001;81:2391.
[23] Ramgopal T, Gouma PI, Frankel GS. Corrosion 2002;58:687.
[24] Ringer SP, Hono K. Mater Charact 2000;44:101.
[25] Stiller K, Warren PJ, Hansen V, Angenete J, Gjonnes J. Mater Sci
Eng A 1999;270:55.
[26] Goerigk G, Haubold H-G, Lyon O, Simon JP. J Appl Crystallogr
2003;36:425.
[27] Goerigk G, Haubold HG, Schilling W. J Appl Crystallogr
1997;30:1041.
[28] Marlaud T, Baroux B, Deschamps A, Chemin JL, Henon C. Mater
Sci Forum 2006;519521:455.
[29] Da Costa G, Vurpillot F, Bostel A, Bouet M, Deconihout B. Rev Sci
Instrum 2005;76.
[30] Danoix F, Miller MK, Bigot A. Ultramicroscopy 2001;89:177.
[31] Vaumousse D, Cerezo A, Warren PJ. Ultramicroscopy 2003;95:
215.
[32] Godard D, Archambault P, Aeby-Gautier E, Lapasset G. Acta Mater
2002;50:2319.
[33] Deschamps A, Brechet Y, Guyot P, Livet F. Z Metallkd 1997;88:601.
[34] Deschamps A, Brechet Y, Livet F. Mater Sci Technol 1999;15:993.
[35] Bakker H, Bonzel HP, Bru CM, Dayananda MA, Gust W, Horvth
J, et al. Diusion in solid metals and alloys. Berlin: Springer Verlag;
1990.