Acta Materialia 51 (2003) 51515158

www.actamat-journals.com

Secondary precipitation in AlZnMg(Ag) alloys

C.E. Macchi a, A. Somoza a,, A. Dupasquier b, I.J. Polmear c
a

Instituto de Fisca de Materials Tandil, IFIMAT, Universidad Nacional del Centro de la Provincia de Buenos Aires and
CICPBA, Pinto 399 B7000GHG Tandil, Argentina
b
INFM and Dipartimento di Fisica, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milan, Italy
c
Department of Materials Engineering, Monash University, Clayton, Vic. 3168, Australia
Received 28 March 2003; accepted 27 June 2003

Abstract
Secondary ageing of age-hardenable aluminium alloys occurs at temperatures below the solvus of GP zones after a
preliminary ageing at a higher temperature. The phenomenon has technological interest, as it may be included in heat
treatments giving a substantial benefit on the mechanical properties. In the present work, positron annihilation lifetime
spectroscopy (PALS) is applied in combination with Vickers hardness measurements for an investigation on secondary
ageing of Al4wt.%Zn3wt.%MgxAg, where x = 0, 0.1, 0.2, 0.3, 0.5 wt.%. Ageing regimes have been characterised
by the substantially different evolutions that are observed. The results shed light on the interplay between the formation
of coherent solute aggregates (clusters or GP zones) and the precipitation of semi-coherent or incoherent precipitates,
which are in competition to control the hardening effects. PALS data show that secondary ageing in the ternary AlZn
Mg alloys produces coherent aggregates even in the presence of a well-developed stage of semi-coherent or incoherent
precipitation that is obtained if the alloys are first aged to peak hardness. In the presence of Ag, on the contrary, the
effects of coherent aggregation during secondary ageing are observed only if the preliminary ageing is interrupted well
before reaching peak hardness.
2003 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Aluminium alloys; Age hardening; Secondary ageing; Positron annihilation spectroscopy

1. Introduction
Alloys based on the AlZnMg system are
widely used in the aircraft industry because of their
high response to age hardening. The complete ageing sequence in a wide range of ternary compositions is: supersaturated solid solutionGP(Zn,

Corresponding author. Tel.: +54-2293-44-2821; fax: +542293-44-4190.

E-mail address: asomoza@exa.unicen.edu.ar (A. Somoza).

Mg)
zones
(hexagonal)
(MgZn2,
hexagonal) [1]. Furthermore, in alloys with relatively high Mg contents, complex cubic precipitate
T, (Al, Zn)49Mg32, may also form. In most ternary
AlZnMg alloys, maximum hardening occurs at
ageing temperatures up to 130 C when the
microstructure consists mainly of Guinier-Preston
zones (GP zones). It has been generally accepted
that the intermediate precipitate nucleates from,
or at the sites of these zones, although recent work
has suggested that this may not necessarily be so
[2]. This work has shown that, for the alloy Al

1359-6454/$30.00 2003 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
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C.E. Macchi et al. / Acta Materialia 51 (2003) 51515158

4Zn3Mg (all compositions in wt.%) aged at 150

C, it is the equilibrium phase T rather than that
precipitates and causes hardening.
Earlier work revealed that microalloying
additions of silver (0.1 wt.%) had the unique
effect of stimulating enhanced age hardening in
ternary and more complex AlZnMg alloys aged
at higher temperatures (120220 C) [35].
Indirect evidence suggested that these effects
might arise because of a preferred interaction
between Ag atoms (possibly in conjunction with
Mg atoms) and vacancies, which stimulates
nucleation of the intermediate precipitates [5].
Recently, atom probe studies on the same alloys
have indicated that early clustering of Zn and Ag
atoms may also be significant [2]. Positron annihilation lifetime spectroscopy (PALS) has also been
applied for the study of the microstructural evolution of alloys Al4Zn3MgxAg (x = 00.5
wt.%) following preliminary ageing at 150 C, in
correlation with Vickers microhardness measurements (HV) [6]. It may be recalled that PALS is an
experimental technique with enhanced sensitivity
to open volumes (vacancies, vacancysolute clusters, misfit at precipitatematrix interfaces). In the
field of age hardening, PALS and other techniques
in the more general family of positron annihilation
spectroscopy (PAS) can be applied to the study of
the vacancysolute interactions, which are crucial
to determining the kinetics of the solute aggregation process, and to the detection of semi-coherent or incoherent precipitation [7].
In the present work, the investigation on AlZn
Mg(Ag) alloys by PALS and HV of Ref. [6] has
been extended to secondary ageing, i.e. the
decomposition stage that occurs at temperatures
below the solvus of Guinier-Preston zones after the
interruption of ageing at a temperature typical of
the T6 temper. The technological interest of secondary ageing stems from the improvement of
mechanical properties that has been obtained for
an extended range of Al-based alloys with novel
multi-stage heat treatments that include secondary
ageing as an intermediate or final stage [810]. The
sensitivity of PALS to secondary ageing was first
observed with AlCuMgbased alloys [11,12];
recently, PALS was used in combination with HV
and differential scanning calorimetry (DSC) for a

detailed study regarding secondary ageing of Al

4Cu0. 3Mg. [13,14]. The present work is the first
application of PALS to the study of secondary ageing in AlZnMg-based alloys.
The paper is organised as follows: Section 2
gives information regarding the details of alloy
preparation and of the experimental methods; Section 3 presents experimental data on ageing at
room temperature occurring as a primary stage, i.e.
immediately following the solution treatment; Section 4 presents data on secondary ageing at room
temperature, in correlation with the alloy conditions reached at the interruption of the primary
ageing at 150 C. In Section 5, a summary of the
main results of the work leads to more general considerations.
2. Experimental
The alloys studied in the present work were the
ternary system Al4Zn3Mg (alloy 4300, composition in at.%: 1.7 Zn, 3.4 Mg) and the quaternary
systems 4301, 4302, 4303, 4305, derived from
4300 with Ag additions from ~0.1 wt.% (~0.026
at.%) to ~0.5 wt. % (~0.13 at.%). These alloys
were prepared using high-purity materials that
were melted in graphite crucibles, degassed, chill
cast and hot forged to produce 6 mm thick strips.
Samples for hardness testing and PALS measurements (1.8 20 20 mm3) were prepared from
these strips by spark cutting and polishing. All
alloys were solution treated at 460 C, quenched
into water at RT, aged for various times in a
glycerine oil bath at 150 C, quenched again and
left to age at 20 C (RT). The lifetime spectrometer
was a fastfast timing coincidence system with a
time resolution (FWHM) of 255 ps. A 20 Ci
source of 22NaCl deposited on a thin Kapton foil
(7.5 m) was sandwiched between two identical
alloy specimens. After subtracting the source
component, the spectra with about 106 coincidences were satisfactorily analysed using the
POSITRONFIT program [15] as a single decaying
exponential (for a discussion on this analysis, see
Refs. [7,16]). Vickers microhardness measurements were performed after each positron lifetime
measurement by using a load of 300 g. Lifetime
spectra and hardness data were always taken at RT.

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3. Results: T4 temper
The T4 temper consists in natural ageing at room
temperature after solution treatment and quenching. It is well-known that AlZnMg-based agehardenable alloys harden at room temperature rapidly during the first 510 h after a solution treatment, and then continue to harden at a much slower
rate. Slow hardening has been observed to continue
for several years at relatively low temperatures.
The present results, depicted in Fig. 1, show that
the increase of the Vickers microhardness HV vs.
natural ageing time can be fitted by a logarithmic
law for more than three decades after 20 min. The
data in Fig. 1 also show the increase of HV due to
Ag as a microalloying addition, and confirm that
this effect is more evident when passing from 0.2%
to 0.3% Ag content [5]. This increase is already
manifesting in the as-quenched values of HV;
further hardening then occurs almost with the same
logarithmic slope (see the data in Table 1). It was
reported previously that hardening at RT is slightly
delayed when Ag is present [4], and the present
results confirm that this effect is marginal into the
range of times studied. Apparently, the small differences in the size and in the distribution of solute
clusters and GP zones, which has been observed
in the ternary and quaternary alloys after ageing at
temperatures below the solvus of GP zones [2],
have no dramatic effects on the hardening behaviour.

Fig. 1. Evolution of Vickers microhardness against natural

ageing time after quenching for Al4Zn3MgxAg (wt.%).

5153

Table 1
Hardening during natural ageing. The logarithmic slopes refer
to the straight line fitting of the data presented in Fig. 1
Ag content
(wt.%)

Logarithmic slope
(VHN/time decade)

0
0.1
0.2
0.3
0.5

15.4
15.0
13.7
13.9
13.4

0.2
0.4
0.1
0.3
0.3

Linear correlation
coefficient
0.997
0.995
0.998
0.998
0.995

Recently, the authors of the present paper have

reported PALS data showing that the evolution of
the positron lifetime at room temperature in Al
ZnMg-based systems proceeds as a Debye-type
relaxation with a time-independent rate [6], in contrast with the Kohlrausch-type behaviour observed
with AlCuMg-based alloys [11,12]. This shows
that the solute aggregation is essentially controlled
by a single diffusing species. Quantitative details
on the evolution of the positron lifetime during
natural ageing will be given below.

4. Results: T6 and T6I4 tempers

4.1. Artificial ageing at 150 C
The T6 temper consists in an artificial ageing
treatment at a temperature that may be above the
solvus of GP zones. In the present experiment, the
treatment temperature was 150 C as in the work
by Vietz et al. [5]. Figs. 2 and 3, regarding respectively Al4Zn3Mg and Al4Zn3Mg0.3Ag,
show HV (lower left panels) and t (upper left
panels) data. The hardness curves of Ref. [5] are
also shown for comparison. The same information
was collected for Ag concentrations x = 0.1, 0.2,
and 0.5 wt.% [6]. Up to x = 0.3%, which is considered to be the limit of solid solubility [4], the
experimental curves scale nicely with x; on the
contrary, the data for x = 0.5% are practically the
same as those obtained for x = 0.3%, as shown by
a few points included in Fig. 3.
The present data confirm the well-known dramatic
effect of Ag microalloying on the hardness and on
the hardening rate [35]. In the present experiment,

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C.E. Macchi et al. / Acta Materialia 51 (2003) 51515158

Fig. 2. On the left side, effects of preliminary ageing at 150 C for the alloy Al4Zn3Mg (wt.%) on positron lifetime (upper panel)
and Vickers hardness (lower panel). Data points from Ref. [7] and solid curve from Ref. [5]. The vertical line at about 90 min marks
the incubation time for initial loss of coherence. On the right side, effects of secondary ageing at RT. The horizontal lines crossing
from the left- to right-side panels connect the points reached after preliminary ageing with the corresponding secondary ageing curves.

peak hardness increases by more than 75%, and is

reached in about 15 h instead of 150 h as for the
ternary alloy. Concerning positron lifetime curves, it
can be said that the behaviour displayed in Figs. 2
and 3 (upper left panels), consisting of an initial rapid
positron lifetime decrease followed by an extended
increasing stage, is typical for most Al alloys
[6,16,17]. The accepted interpretation of the two
stages is [6,1618]: (a) the initial decrease is associated with the formation of coherent aggregates, which
gradually absorb the mobile vacancysolute complexes; (b) the increasing stage is due to the formation of misfit interfaces between the matrix and semicoherent (or incoherent) precipitates. Coarsening of
the precipitates after long ageing times (not reached
in the present experiments but observed in the pre-

vious works mentioned above) would give a third

stage of decreasing positron lifetime. The times when
the minima for the curves depicted in Figs. 2 and 3
are reached can be taken as an operational definition
of the incubation time for the loss of coherency (for
more details, see Ref. [6]). A vertical line drawn
through the minimum of the positron lifetime curves
shows that the incubation time derived from PALS
data corresponds to the beginning of the hardening
stage. This leaves no doubts that hardening at 150 C
is related to the precipitation of incoherent or semicoherent particles. This mechanism is referred to
below as incoherent or semi-coherent regime, as
opposed to the coherent regime occurring when
hardening is obtained without loss of coherency.
The present results show that presence of Ag does

C.E. Macchi et al. / Acta Materialia 51 (2003) 51515158

5155

Fig. 3. On the left side, effects of preliminary ageing at 150 C for the alloy Al4Zn3Mg0.3Ag (wt.%) on positron lifetime (upper
panel) and Vickers hardness (lower panel). Data points from Ref. [7] and solid curve from Ref. [5]; open points are measured for
x = 0.5 at.% Ag. The vertical line at about 8 min marks the incubation time for initial loss of coherence. On the right side, effects
of secondary ageing at RT. The horizontal lines crossing from the left- to right-side panels connect the points reached after preliminary
ageing with the corresponding secondary ageing.

not modify the type of regime, although it strongly

affects kinetics and the morphology of the precipitation. This is consistent with recent results of
HRTEM and 3D-AP experiments [2], showing
that, in the ternary alloy with the same composition
as in the present work (Zn:Mg atomic ratio
0.5), precipitation consists of the equilibrium cubic
T phase, whereas in the presence of 0.1 at.% of
Ag the loss of coherency occurs most probably by
nucleation of the phase from solute clusters with
a Zn:Mg ratio near to 1. The finer dispersion of
particles is seen as the reason for the increased
hardness. However, it must be observed that the
extreme sensitivity of PALS to any structure asso-

ciated with open volumes enables one to observe

an initial loss of coherency much earlier (less than
10 min at 150 C for alloys 4303 and 4305) than
the stage when particles can be directly
observed by electron microscopy (2 h at 150 C
for alloy 4305 [2]).
4.2. Secondary ageing at 20 C
The T6I4 temper (I = interrupted), described in
detail in Ref. [10], consists in a two-stage thermal
treatment. In the first stage (preliminary ageing)
the sample is held at a temperature above the
solvus of GP zones (150 C in the present

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C.E. Macchi et al. / Acta Materialia 51 (2003) 51515158

experiment) for a short period of time relative to

a full T6 temper, thereby producing an underaged
alloy. Depending on the duration of the first stage,
primary hardening precipitation develops to different levels. The first stage is then interrupted by
quenching at RT, to retain a maximum supersaturation of residual solute and vacancies. The second
stage of the T6I4 temper is secondary ageing,
which is of particular interest in the present investigation. The right panels of Figs. 2 and 3 show the
kinetics of hardness and positron lifetimes during
the secondary ageing process, for different durations tpa of preliminary ageing. The horizontal
lines crossing from the left to the right panels connect each secondary ageing curve with the corresponding point at the end of the preliminary ageing. The time co-ordinate of this point gives the
appropriate tpa value for the secondary ageing
curve. Similar data were also collected for silver
concentrations x = 0.1, 0.2, and 0.5 wt.%. From
x = 0% to 0.3% all results scale smoothly; the case
x = 0.5% is very similar to that for 0.3%. The
analysis and discussion of the different evolutions
are considered below.
4.2.1. Coherent regime at RT (t pa = 0)
This is just natural ageing at 20 C, due to the
formation of coherent structures (clusters and then
GP zones), which has been discussed above. Fig.
2, regarding the ternary alloy, shows that natural
ageing results in a decrease of the positron lifetime
from t 0~208 ps toward an asymptotic value
t ~202 ps, whereas there is an increase of the
hardness from 57 VHN to about 105 VHN (in
accordance with Fig. 1). The comparison with the
left panel helps to note that the final value of the
hardness is above the level obtained with a full T6
temper at 150 C (85 VHN). Fig. 3 shows very
similar behaviour of the hardnesstime curve for
the quaternary alloy. However, in this case, the
maximum hardness reached with natural ageing is
well below the peak hardness obtained with the
treatment at 150 C. The positron lifetime curve
for the quaternary alloy differs from that of the
ternary alloy essentially because of the lower value
of t (~196 ps instead of 202 ps). The reason can
be the presence of Ag near to the vacancies trapped
inside the solute clusters. The concentration of Ag

in these clusters is known to be well above the

average concentration of the alloy [2].
4.2.2. Predominantly coherent regime (early
primary ageing: tpa from 10 to 120 min for x = 0
and from 2 to 10 min for x = 0.3%)
Positron lifetimes show a non-monotonic behaviour beginning below t0, but still ending near to
t. Similar non-monotonic trends have been
observed for AlCuMg-based alloys, and have
been attributed to the changing chemical composition of vacancysolute aggregates, due to a different temperature dependence of the aggregation
kinetics of Cu and Mg [11,12]. The same explanation can be applied to the present situation, with
Zn playing the same role as Cu. The initial point
of each HV curve increases slightly with tpa, but
the strongest increase occurs during the secondary
ageing, up to a final point still around 105 VHN.
Note that this stage includes the incubation time
for the loss of coherence (about 90 min). The
changes in hardness and positron lifetime occurring after this limit can include an irreversible contribution from semi-coherent/incoherent particles.
However, the final values reached after secondary
ageing, which are the same as without preliminary
ageing, show that this contribution is negligible in
comparison with that due to new coherent structures formed at RT because of the residual supersaturation of solute.
4.2.3. Transition regime (intermediate primary
ageing: tpa from 120 to 1000 min for x = 0)
Due to the rapid onset of precipitation in the
presence of Ag, the intermediate stage was
observed clearly only for the ternary alloy. The
positron lifetime in this alloy decreases monotonically, indicating the formation of coherent structures. However, the initial point, at the end of the
preliminary ageing, is above t0 and the final value
is also above t. Most probably, this is the effect
of positron trapping at the misfit surfaces of semicoherent or incoherent precipitates, which is not
anymore negligible in comparison to trapping at
vacancies inside coherent structures. The effect of
precipitation during the preliminary ageing on the
HV curves is also evident in the increase of the
initial point of HV. However, the hardness value

C.E. Macchi et al. / Acta Materialia 51 (2003) 51515158

reached after long secondary ageing is essentially

the same obtained with the simple T4 temper.
Clearly, the hardening effect of coherent zones formed from the residual supersaturation after the preliminary treatment is the dominant one.
4.2.4. Incoherent (semi-coherent) regime at 150
C (tpa from 360 min for x = 0 and from 60 min
for x = 0.3%)
For the ternary alloy, the hardness curves reach
a peak value at 85 VHN. With long ageing times,
the formation of semi-coherent or incoherent precipitates leaves almost no residual solute for producing additional hardening due to further coherent
aggregation. However, the small decreasing trend
of the positron lifetime curves (from 218 to 215
ps) demonstrates that some structural evolution
still occurs during secondary ageing. Most probably, this is due to a slight excess of solute because
of the solubility change with the temperature that
gives a degree of supersaturation sufficient for forming a small concentration of new coherent zones.
The changes of the positron lifetime that are
observed during the secondary ageing would thus
be due to a balance of effects between coherent
and incoherent particles in competition. In the
presence of Ag, the situation appears different:
during the RT stage, HV and t remain constant at
values depending only on tpa. This means that the
strong effect of semi-coherent or incoherent particles becomes rapidly dominant, even if the treatment at 150 C is interrupted before peak ageing. If
any coherent structure is formed during secondary
ageing, this has not been detected using the characterisation techniques adopted in the present work.

5. Conclusions
The main results of the present work come from
the correlation between hardness and positron lifetime curves, and from the observation of effects
of secondary ageing at 20 C that occur following
different periods of preliminary ageing at 150 C.
They can be summarised as follows:
The incubation time for the loss of coherency
is unambiguously determined from positron life-

5157

time curves taken during artificial ageing at 150

C; it marks the separation between a coherent
regime (temporary formation of solute clusters
and GP zones), which gives no significant hardening at this temperature, and the onset of the
incoherent regime, corresponding to a rapid
increase of HV.
Secondary ageing effects at RT are observed for
the ternary as well as for the quaternary alloys,
with features depending on the duration tpa of
the preliminary ageing.
For tpa below a certain critical time, which is
greater than the incubation time mentioned
above, one has the coherent regime. In this
regime, the formation of new solute clusters and
GP zones becomes dominant over the small
concentration of semi-coherent or incoherent
particles formed during the preliminary treatment. Further hardening occurs up to levels significantly higher than at the end of the preliminary ageing.
In the coherent regime, the non-monotonic
trends of the positron lifetime curves indicate
that the chemical composition of solute clusters
and GP zones formed during secondary ageing
at RT is different (probably with higher Mg
content) from the composition of the structures
formed during the preliminary ageing.
For tpa above the critical time, one can have an
intermediate regime or, in a more abrupt way,
pass directly to the incoherent regime, where
hardening effects become weaker or disappear.
In this case, the precipitates formed during the
preliminary ageing are dominant. However, a
small decrease of the positron lifetime, observed
at least for the ternary alloy, shows that limited
formation of coherent zones may still occur.
This is an interesting result, since the excess solute, still present after the formation of incoherent precipitates, might be expected to be simply
absorbed into the existing precipitates without
nucleating new coherent structures.
The presence of Ag, which gives a small initial
reduction of the hardening rate at RT, accelerates the precipitation at 150 C. It is known that
this is due to the precipitation of finely distributed particles [2].

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C.E. Macchi et al. / Acta Materialia 51 (2003) 51515158

From the above results, it is possible to draw

some general indication regarding secondary ageing phenomena. It is clear that the key factor controlling hardening effects is the balance between
precipitates formed during the preliminary ageing
and the coherent aggregates (solute clusters and GP
zones) nucleated during subsequent secondary ageing. This balance depends on the level of residual
supersaturation of solute and vacancies remaining
after preliminary ageing, and the relative hardening
associated to coherent aggregates on the one hand,
and to semi-coherent or incoherent precipitates on
the other hand. In the present work, the comparison
of AlZnMg and AlZnMgAg was instructive
on this aspect.

Acknowledgements
A. Somoza and C. Macchi acknowledge the financial support of the Consejo Nacional de Investigaciones Cientficas y Te cnicas (PIP/BID
N4318/97), Agencia Nacional de Promocio n
Cientfica y Tecnolo gica. (PICT N 0192/97),
Comisio n de Investigaciones Cientficas de la Provincia de Buenos Aires and Secretara de Ciencia
y Te cnica (UNCentro), Argentina. A. Dupasquier
acknowledges the financial support of the Ministero dellIstruzione, Universita` e Ricerca (FIRB
2001).

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