Philosophical Magazine Part B

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A study of the high-temperature ageing of Al-Cu-

Mg-Ag alloy 201

S. Abis , P. Mengucci & G. Riontino

To cite this article: S. Abis , P. Mengucci & G. Riontino (1993) A study of the high-temperature
ageing of Al-Cu-Mg-Ag alloy 201, Philosophical Magazine Part B, 67:4, 465-484, DOI:
10.1080/13642819308207686

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 PHILOSOPHICAL
MAGAZINE
B, 1993, VOL.67, No. 4, 465484

A study of the high-temperature ageing of

Al-Cu-Mg-Ag alloy 201

By S. ABIS
Federal Mogul S.p.A., Federal Mogul Corporation, Via Trione 5,
10082 Cuorgne‘ (TO), Italy

P. MENGUCCI
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Dipartimento di Scienze dei Materiali e della Terra,

Universita di Ancona, Via Brecce Bianche, 60131 Ancona, Italy

and G. RIONTINO
Dipartimento di Chimica Inorganica, Chimica Fisica e Chimica dei Materiali,
Universita di Torino, Via Giuria, 9-10125 Torino, Italy

[Received I4 August I992 and accepted 23 September 19923

ABSTRACT
The microstructural evolution of At-Cu-Mg-Ag alloy 201 during ageing at
190°C after solution treatment, quenching and room-temperature annealing has
been investigated by a joint differential scanning calorimetry and transmission
electron microscopy (TEM) analysis, with the aim of clarifying the early stages of
R-CuAI, precipitation.
After room-temperature ageing, the TEM observations show the presence of
both copper Guinier-Preston zones (GPZs) and a phase exhibiting a hexagonal
structure with lattice parameters a=0.507 nm and c=O.692 nm, here called R’. At
this stage, the (1 1l)Al zone axis electron diffraction pattern exhibits a structure
completly different from those reported in literature when the 0 phase is present.
This pattern can be interpreted by taking into account the GPZ and R’ structures.
During ageing at 190°C the copper GPZ formed at room temperature
immediately disappear while the well known precipitation sequence @”_*@’ occurs.
At the same time, R’ slowly disappears while R precipitates appear on { l l l f A l
planes. After 60min at 190”C, R particles are clearly visible but R’ is still present.
S’ (CuMgAl,) precipitates appear after only 60min at 190°C. They are
heterogeneously nucleated on defects and a copious precipitation occurs after only
ageing for 10 h.
The present results suggest that the early phase, here named R’, is the precursor
of the Il-CuAI, phase typical of this family of alloys. The whole precipitation
sequence at 190°C is therefore
u,,,+GPZ +a+@’
+a+@’’ + R + S’.

6 1. INTRODUCTION
It is well known that the age-hardening behaviour of Al-Cu-Mg alloys having a
copper content of about 4.5 wt% and a high copper-to-magnesium ratio is character-
ized by the precipitation sequence
a,,,+GP+GPB+O”+ S’+O’+ S’+O + S,
where asssis the supersaturated solid solution obtained by quenching the alloy from the
solutioning temperature, GP are the copper Guinier-Preston zones (GPZs), GPB
0141-8637/93 $lONI 0 1993 Taylor & Francis Ltd.
 466 S. Abis et al.

are the copper-magnesium GPZs, @"(orGPII) are three-dimensional copper GPZs, S'
is a precursor of the equilibrium phase CuMgAl,, 0' is a semicoherent precursor of the
equilibrium phase CuAl,, S is the equilibrium phase CuMgAl, and 0 is the equilibrium
phase CuAl,.
Depending upon the ageing temperature, the precipitation can proceed following
the whole sequence or, at higher temperatures, the simplified path
01,,,+@" + S'+@' + s -+@ + s.
The structure and characteristics of these phases have been widely studied and well
identified in the past (Silcock, Heal and Hardy 1953-1954, Laird and Aaronson 1966,
1968, Lorimer 1978.)
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It has also been noted (Polmear 1964,Vietz and Polmear 1966)that a small amount
of silver added to the alloy (say 0.6-07 wt%) can modify the precipitation process,
giving also a noticeable increase in the hardening response.
Alloys of commercial interest based on Al-Cu-Mg-Ag compositions, namely
KO-1 in the USA (now called aluminium alloy 201) (Iler 1969) and AVIOR in
France (Speidel 1975) having an addition of 1.2 wt% Zn, have been developed.
Aluminium alloy 201 has a nominal composition A14.5 wt% Cu-0.35 wt%
M g 0 7 wt% Ag-O.35 wt% Mn; it is claimed that premium castings in the T7 condition
can reach a yield strength and an ultimate tensile strength as high as 450 and 500 MPa
respectively. Therefore the study of the precipitation phenomena in the commercial
alloys is of primary importance.
Chester and Polmear (1981) studied the relationship between microstructure and
properties in alloy 201; they investigated the distribution of metastable phases for
different ageing times at temperatures between 150 and 200"C, performing also a
qualitative comparison between silver-containing and silver-free alloys by differential
scanning calorimetry (DSC).
The hardening increase has been linked to the precipitation of a new phase not
present in the precipitation sequence of the silver-free alloy (Auld and Vietz 1969):the
so-called R phase.
The structure and composition of the R precipitate have been studied by Knowles
and Stobbs (1988), by Muddle and Polmear (1989) and more recently by Garg and
Howe (1991).It is accepted that R has an orthorhombic structure that can be regarded
as a distortion of the tetragonal @-CuA1, phase typical of binary averaged Al-Cu
alloys, having also the same chemical composition and the orientation relationships
[oollQll[ll llAi,
[ololQlloilAi,
C1O01Q 11 [Iz l]Ai.
Garg and Howe (1991)proposed that the R-phase can be considered as a variant of the
equilibrium @-phase,called OM, having a tetragonal structure with lattice parameters
a = 0.6066 nm and c = 0.496 nm and the following orientation relationships with the
matrix:
[ilol@Mlt[llllAb

[lloI@~II[loilAb

[0011t3~~~[12T1Al*
 High temperature ageing of Al-Cu-Mg-Ag 467

Muddle and Polmear (1989) reported that

(1) silver partitions in R precipitates during ageing while it does not in 0 and/or
o',
(2) silver may segregate at the matrix-precipitate interface and
(3) there is a good evidence of a magnesium association with R even if results are
not yet conclusive.
Actually, Sano, Hono, Sakurai and Hirano (1991) observed that both silver and
magnesium atoms segregate at the interphase interfaces.
The interesting problem of R formation and the role of silver in promoting the
precipitation of the new phase have also been considered; in particular, Taylor, Parker
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and Polmear (1978) suggested that an early Mg,Ag precipitate appearing on (111)
planes might be the precursor of R and that it can collect copper atoms during later
stages of ageing, approaching a composition close to CuAl,. Nevertheless the suggested
phase Mg,Ag has not been observed, and a paper by Cousland and Tate (1986)dealing
with aluminium-rich Al-Mg-Ag alloys, reported the formation of MgAg GPZs.
Recently, Garg, Chang and Howe (1990) observed the formation of the R phase in an
Al-Cu-Mg alloy in the absence of silver, suggesting that silver is not necessary for the
nucleation of R. Nevertheless, in the same alloy, the precipitation of the R-phase was
drastically enhanced at the expense of 0'by the addition of 0 5 wt% Ag.
A complete understanding of the precipitation mechanism of the R-phase is still a
matter of debate, even if a commercial alloy based essentially on a R-strengthening
mechanism has been reported (Polmear and Couper 1988).
In the present paper we report the results of the study of the age-hardening
mechanisms in a commercial alloy A201 aged at 190°C after solution treatment,
quenching and annealing at room temperature for 24 h. The ageing process is studied
during increasing ageing times, up to peak ageing, starting from the T4 temper, in order
to detect early formation of the R-phase.
DSC has been used to detect the presence of different phases after a given thermal
treatment, while transmission electron microscopy (TEM) observations were able to
supply information on the nature and structure of the different phases.

$2. MATERIALS AND METHODS

Pure aluminium and silver, and Al-Si, Al-Mg and Al-Cu master alloys were melted
in an electrical furnace; the chemical composition of the molten charge is reported in
table 1.
Cylindrical specimens 250mm in length and 20mm in diameter were cast in
permanent die after degassing and refining of the molten bath.
Cast specimens were homogenized at 500°C for 3 h followed by 3 h at 515°C and
finally 22 h at 530°C. Samples were then quenched in water at 20°C and held at room
temperature for 24 h before ageing.
Ageing treatments were performed at 190 rf: 1°C in a thermostatic silicone-based
bath for 15, 60 and 600 min.

Table 1. Chemical composition of the investigated alloy.

Element Cu Mg Mn Ag Fe Si Ti A1
Amount (wt%) 4 5 0.31 0.34 0.7 0.07 0.04 0.22 Balance
 468 S. Abis et al.

Fig. 1
150

125

HB 100

75
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50
1 10
Ageing time (hours)
Brine11 hardness values against ageing time at room temperature (r.t.) and at 190°C.

Slices 1mm thick were cut from the samples for TEM analysis, while small cylinders
5 mm in diameter were machined under a coolant flow for DSC.
TEM specimens were prepared by grinding papers and diamond polishing paste.
Final thinning was performed in a double-jet unit with a 30% HN0,-methanol
solution at - 35°C and 15V. Observations were carried out in a Philips CM12 electron
microscope at 120kV. Selected-area diffraction pattern (SADP) and microdiffraction
techniques were used in order to study the structure of the precipitates and their
orientation relationships with the matrix.
Small slices l m m thick carefully cut under a coolant flow from the machined
cylinders were used as specimens for calorimetric measurements; they were performed
in a Perkin-Elmer DSC-7 instrument under an argon atmosphere at five different
scanning speeds, namely 5, 10, 30, 70 and 100 K min.

$3. RESULTS
Hardness measurements (fig. 1) show a monotonic increase as a function of time,
starting from the quench value. The curve obtained at 190°C after annealing for 24 h at
room temperature indicates the presence of a maximum (T7) after ageing for 10 h.
DSC measurements have been carried out on the T4 temper (24h at room
temperature) and on the T7 condition (peak hardness). Two other tempers have been
considered between T4 and T7 in order to follow the evolution of precipitation
hardening, namely T4 + 15 min at 190°C and T4 + 60 min at 190°C.DSC results will be
presented in three different sections, each referring to the tempers investigated.

3.1. T4
The thermograms obtained for the T4 temper, reported in fig.2, show a very
complex path, several exothermal and endothermal effects being present in the scanned
temperature range.
(1) A first endothermal effect, labelled A, is present below 100°C; its peak
temperature moves towards higher values as the scanning speed is increased
 High temperature ageing of Al-Cu-Mg-Ag 469

Fig. 2
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I I I I I
100 m 300 400 500
Temperature (OC)
Thermograms obtained for the T4 temper; the different scanning rates are indicated in K min- '.

from 10 to 100 K min-', indicating that the process relative to A is thermally

activated.
(2) An exothermal effect labelled B follows between 100and 150°C;also in this case
the position of the peak temperature is an increasing function of the scanning
speed.
(3) A second endothermal effect labelled C lies at about 200°C; it refers to a
thermally activated process as are the previous processes.
(4) Between 250 and 350°C a large exothermal effect can be found; from the
observation of all the thermograms obtained at different scanning speeds, it is
quite evident that the whole effect can be resolved in three different peaks
partially superimposed, which have been labelled D, E and F; since they relate
to thermally activated processes, they appear as a unique effect at the lowest
scanning speeds.
(5) Between 400 and 510°C (the solution treatment temperature), a large and
spread endothermal effect can be observed. Displacements of peak tempera-
tures by changing the scanning rate are not detected in this range.
 470 S. Abis et al.

Fig. 3
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I I I I I
103 m 300 400 500
Temperat unz(OC)
Evolution of DSC thermograms between the T4 and T7 tempers (scanning rate, 30 K min- ').

3.2. Evolution between T4 and T7 (15 and 60min at 190°C)

After ageing for 15 min at 190°C, following the anneal at room temperature, the
thermograms (the trace obtained at 30 K min-' is reported in fig. 3) show several
modifications with respect to the T4 temper, namely
(1) the endothermal effect A and the exothermal effect B have disappeared,
(2) the peak temperature of the endothermal effect C is increased and
(3) the relative intensities of the effects D, E and F are decreased.
The traces obtained after ageing for 60min at 190°C exhibit the same trend just
described; A and B are no longer visible and once again the peak temperature of C is
increased. Moreover the effect F is no longer detectable, the lower temperature section
of G appears to be increased, and its evolution begins at about 300°C.

3.3. T7
Thermograms obtained for the T7 temper show marked differences with respect to
the previous thermograms (the 30 K min- thermogram has been reported in fig. 3).
 High temperature ageing of Al-Cu-Mg-Ag 47 1

The results show that only two exothermal effects can be detected:
(1) peak C which now ranges between 200 and 250°C depending upon the
scanning speed;
(2) effect G, whose starting temperature is now placed near 280°C.
The exothermal effects D, E and F are no longer detected.

0 4. DISCUSSION
Even if not very common in metallurgical research, DSC is able to give interesting
information which completes other data obtained from more frequently used
techniques as TEM or hardness measurements, This is true especially in the field of
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phase transformations; in this case, DSC measurements supply two kinds of

information.
(Q) A given distribution of phases, determined by the thermomechanical history of
the investigated material, is destroyed during a temperature scan. The
endothermal and/or exothermal effects obtained can be assigned to dissolving
and/or precipitating phases. In this way conclusions can be drawn about the
phases present before the scan.
(2) A solution-treated-and-quenched material is subjected to a temperature scan.
If the scanning speed is correctly adjusted and sufficiently slow, all the
precipitation sequence is displayed during the scan as exothermal and
endothermal effects.
Obviously DSC is not able to assign a given thermal effect to a specific phase, and
the DSC investigation must be integrated with other techniques, for example TEM.
Moreover the thermograms can be compared with other traces from the literature (e.g.
X-ray) or simplified systems which undertake transformations involving one or more
phases of the same kind of the system under investigation.
The DSC results will be therefore discussed with the aid of TEM observations and
data from the literature.
TEM observations and electron diffraction patterns have been typically taken from
the three main zone axes of the matrix, namely (001), (011) and (111).
An analysis of the thermogram relative to the T4 temper, starting from lower
temperatures, firstly shows an endothermal effect A. It refers to a dissolution
phenomenon taking place during the temperature scan and must be assigned to the
dissolution (maybe a partial reversion) of phases formed during ageing at room
temperature.
The following exothermal effect B indicates that precipitation is taking place during
the scan; the precipitates dissolve at a higher temperature, giving as a result the
endothermal peak C .
The subsequent exothermal effects D, E and F refer, as for B, to the precipitation of
three different phases during the scan, while the endothermal peak G is relative to the
final solutioning of precipitates.
The electron diffraction pattern from a (001),, zone axis of the T4 sample (fig. 4)
shows elongated streaks along [loo],, directions; the pattern of the streaks is
continuous and shows a maximum corresponding to (200)A,reflections. This trend is
typical of a uniform pre-precipitation of elongated plate-like coherent copper GPZs
having the relationship [001]A,(([OOl],p; their size ranges below 5 nm ascan beinferred
from the diffusion of the streaks (Phillips 1975, Rioja and Laughlin 1977, Papazian
 472 S . Abis et al.

Fig. 4
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SADP of the T4 sample from the (001) matrix zone axis; elongated streaks along [loo] typical of
the presence of GPZs are clearly visible.

Fig. 5

(4 (b)
SADPs of the T4 sample: (a)(1 1 I),, zone axis; (b)after tilting 6" from (1 1 along the [0TllAl
direction.
 High temperature ageing of Al-Cu-Mg-Ag 473

1981). A detailed analysis of this pattern shows that extra spots from other phases are
not detectable and, in particular, that the spots characteristic of the R-phase located at
3220) are completely absent.
The most interesting diffraction pattern has been obtained from the (1 1l)*, zone
axis (fig.5 (a)).The distribution of spots in this pattern is completely different from those
reported when the R phase is present, as can be inferred from the comparison with
fig. 17. Following suggestions in the literature we tried to index this pattern by
considering two different phases: hexagonal AgMg, (Taylor, Parker and Polmear
1978) and cubic AgMg (Cousland and Tate 1986). Attempts made with these phases
failed since the interplanar distances of these precipitates are very different from those
obtained by the diffraction pattern.
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Further attempts have been made to index such a pattern by considering the phases
characteristic of the Al-Cu-Mg system reported by Villars and Calvert (1989). In
particular, the presence of the AI,Cu,Mg, phases were carefully investigated in order to
clarify the role of magnesium during the nucleation and growth of the hardening
phases. Although a great number of phases were considered, these investigations failed
to index the diffraction pattern.
These results, and the observation that the (111) electron diffraction pattern of the
alloy during ageing develops into one typical of the R-phase, suggest the presence of a
precursor of this latter during the early stages of ageing.
Very interesting results were obtained by tilting the specimen away from the (111)AI
plane towards the (233),, plane along the [Oil] direction.
The electron diffraction pattern of the specimen tilted 6" from the (111)AI plane
along the COT11 direction is reported in fig. 5 (b).Since the angle between the (11l),, and
the (233),, planes is 10.02",the specimen orientation, in this case, becomes closer to the
(233),, plane. The regular distribution and the uniform intensity of the spots in this
pattern indicate that this orientation represents the precipitation plane of the
precursor, here named R'.
The diffraction pattern can be attributed to the [122] direction of a hexagonal R'
phase with the lattice parameters a = 0.507 nm and c = 0.692 nm. The orientation
relationships between the proposed R' precipitate and the aluminium matrix is then
given as [01 1ln.II[31 l],, and [2TO]n.II[OT1]AI.
If one compares the lattice parameters of the proposed R' precipitate with those of
the phases reported by Villars and Calvert (1989) for the Al-Cu-Mg system, one can
infer that a phase exists which has the same crystallographic structure and the same
value of the lattice parameter a, but a different c value with respect to R'. This is a low-
temperature hexagonal phase, of structure type MgZn,, space group P6,/mmc and
Pearson symbol hP12, having a composition Al,Cu,Mg in the range x = 1.8-1.2,
y = 0.92-0.8 and the lattice parameters a = 0507 nm and c = 0.829 nm. These para-
meters are given for x = 1.08 and y = 0.92.
Such an observation suggests considering the proposed R' precipitate as a slight
modification of the above Al,Cu,Mg phase reported by Villas and Calvert (1989). The
difference in the c value could be connected to a different relative concentration of the
elements and/or to the presence of silver in the crystal lattice of R'.
In order to determine the nature of the extra spots in terms of the precipitated
phases, a dark-field image was taken with the spot arrowed in fig. 5 (a).The micrograph
shows a very fine distribution of particles inside the aluminium matrix having mean
dimensions of 5 nm (fig.6). These particles evolve in the well known R-phase as
precipitation proceeds.
 474 S. Abis et al.

Fig. 6
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Dark-field image of the fine distribution detectable in the T4 temper taken with the arrowed spot
of the previous figure.

From the results obtained so far, one can conclude that, after room-temperature
ageing, the alloy shows the presence of both copper GPZs and a phase, here named R',
exhibiting a hexagonal structure. The information available is not able to clarify the
nature of this latter precipitate; nevertheless it could be a slight modification of a phase
belonging to the Al-Cu-Mg system. The microstructural evolution of the alloy during
ageing at 190°C indicates that Q' should be the precursor of the Q phase. Further work
on this is now in progress.
In order to clarify which kind of phase is dissolving during the evolution of peak A, a
sample in the T4 temper has been subjected to a linear temperature rise up to 150°Cat a
scanning speed of 30 K min- followed by a rapid temperature decrease (at about
200 K min- ') in the DSC cell.
The sample has been then observed by TEM. The patterns obtained are similar to
those obtained in the condition T4 + 15 min at 190°C discussed in the following. They
show the presence of 0"and 0'precipitates, confirming that peak A is due to GPZs
formed at room temperature which disappear during the scan up to 150°C. A ( 1 12)A,
zone axis pattern of this sample is reported in fig. 7. Extra spots located at 8311) are
clearly visible. These spots have been indexed as the (011) reflection of the R'phase. On
the other hand, this type of spot has been reported by Knowles and Stobbs (1988)to be
due to the intersection of the Ewald sphere with the streaks generated by the
precipitation ofthe Q-phase on { 11 planes. Therefore it is possible that the Q-phase,
or a variant of it at least, is present in the sample at this stage.
On the basis of TEM analysis one can conclude that the first dissolution peak must
be assigned to the dissolution of the GPZs formed at room temperature, or to a
complex phenomenon comprising a partial reversion of the GPZs superimposed on the
subsequent precipitation phenomenon which will be explained later. A similar result
 High temperature ageing of A1-Cu-Mg-Ag 475

Fig. I
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SADP taken from the ( 1 12) matrix zone axis relative to the T4 sample subjected to a linear
temperature rise to 150°C.

Fig. 8

(4 (4
Sample aged for 15min: (a) diffraction pattern from the <OOl) matrix zone axis; (b) bright field
showing the 0"particles.
 476 S. Abis et al.

Fig. 9
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Diffraction pattern taken from the ( 1 1 1 ) matrix zone axis of the sample aged for 15 min.

has already been noticed for a commercial Al-Cu alloy AA2219 which had undergone
age hardening similar to an high-purity A1-Cu binary alloy (Riontino and Abis 1991).
After ageing for 15 min at 190"C,peaks A and B had disappeared. This can be easily
explained by considering that precipitates formed at room temperature, responsible for
peak A, had been redissolved during the anneal at 190"C,when precipitates responsible
for peak B were formed: therefore effect B, relative to a precipitation during the
calorimetric scan for the T4 temper, cannot be seen.
Moreover peak C , because of the dissolution of the precipitates formed at 190°C is
now displaced towards higher temperatures, indicating that these precipitates have a
higher thermal stability than those formed during the scan of the T4 sample.
It is also important to evidence that exothermal effects D, E and F, relative to the
precipitation of three different phases, are less marked after 15 min at 190°C than in the
T4 thermogram. This has to be linked to a partial precipitation of these phases during
the 190°C ageing.
The diffraction pattern of the sample aged for 15min taken from the (Ool),, zone
axis (fig. 8 (a)) shows streaks having an intensity maximum centred on (loo),,
reflections; this indicates that the tetragonal @"-CuAl, phase with the lattice
parameters a = 0404 nm and c = 0768 nm has already started to precipitate and it is
present inside the aluminium matrix (Papazian 1981).The presence of 0"precipitates
confirms that peak B (which has now disappeared) must be assigned to their
precipitation (and therefore peak C to their dissolution), while the absence of the
dissolution peak A ensures that GPZs formed at room temperature are no longer
present; fig. 8 (b)(zone axis, (OOl)Al) shows 0'' particles lying along the two [010]A] and
[1Oo)AI perpendicular directions.
The diffraction pattern from the (01 l),, axis shows streaks typical of 0" positioned
along the [loo],, direction; extra reflections from secondary phases are not detectable.
 High temperature ageing of Al-Cu-Mg-Ag 477

Fig. 10
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(a) (b)
Sample aged for 60min: (a) diffraction pattern taken from the (001) matrix zone axis; (b)dark
field showing 0‘and 0”precipitates ( - 29, g = (200)).

The (1 1l)A, pattern (fig. 9) is similar to the previously reported T4 pattern, but
several reflections are weaker when compared with these for T4. Moreover several
weak reflections that can be. attributed to the presence of the a-phase, as will be
discussed later, can be observed. It can therefore be concluded that nl is still present
after 15min at 190”C, but the Q particles have already started to nucleate. The electron
diffraction pattern from a (21 l)Alzone axis shows faint spots located at f, -3, 1 and
_-i, - 1, f, which are due to the variants of the Q-phase formed on the (1 11)and (171)
matrix planes respectively (Knowles and Stobbs 1988). Moreover, spots linked to the
presence of 0”phase are visible at 0, - 1, 1.
The same trend detected after 15 min is shown in the thermogram obtained after
60min at 190°C. The effects A and B are not present, the peak temperature of C is
increased and the height of the exothermal peaks D, E and F is decreased; in particular
peak F is no longer detectable.
The diffraction pattern of the sample aged for 60min taken from the (OOl),, zone
axis (fig. lO(a)) shows quite clearly elongated streaks having intensity maxima
corresponding to planes; the streaks are due to the presence of the 0”phase;
reflections at $(220)A, are typical of 0’while the spots at 3220) are typical of the
Q-phase.
The diffraction supplies the following orientation relationships between Q and 0’:

as already seen by Knowles and Stobbs (1988).

A dark-field image taken from the -2g(g =(200)) reflection (fig. lo@))shows the R
and 0’and/or 0”particles.
 478 S. Abis et al.

Fig. 1 1
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(4 (b)
Sample aged for 60min: (a)diffraction pattern taken from the (01 1) matrix zone axis; (b)bright
field showing the 0’ and/or 0”and Q precipitates.

Fig. 12

Diffraction pattern taken from the (1 11) matrix zone axis for the sample aged for 60min.

The pattern taken from (01 l)*, (fig. 1 1 (a))exhibits streaks elongated along [111]*,
which are due to the presence of the Q-phase. They were not detectable in the
corresponding pattern taken after ageing for 15 min, confirming that after ageing for 1 h
the size of SZ precipitates is comparable with those of 0’.
Moreover secondary-phase reflections are now present, indicating that an ordered
phase is dispersed inside the aluminium matrix. Indexing has been carried out on the
basis of the orthorhombic lattice with a =0.496 nm, b = 0.859 nm and c = 0.848 nm, so
obtaining the orientation relationships already reported by Muddle and Polmear
(1989).
 High temperature ageing of Al-Cu-Mg-Ag 479

Fig. 13
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Sample aged for 60min. S’ particles nucleated on defects are clearly visible.

A bright-field image taken from the (01 l)A, zone axis (fig. 1 1 (b))shows both 0’
and/or 0”and R particles, this latter having a mean dimension of 15 nm.
The pattern taken from (1 1l)A,and reported in fig. 12 shows reflections located at
3220) characteristic of the R-phase. In this pattern it is also possible to detect
reflections which have been previously attributed to R’, thereby indicating that this
latter is still present after ageing for 1 h at 190°C.
The presence of S’ (CuMgAl,) cannot be inferred from the analysis of the diffraction
pattern, but it can be directly observed to be nucleated on dislocations (fig. 13);
diffraction reflections are probably masked by 0’(Gupta, Gaunt and Chaturvedi
1987).
The presence of 0‘particles evidenced by diffraction patterns and the contempor-
ary weak presence of S’ precipitates should indicate that peak F must be linked to the 0’
precipitation; as far as the @’precipitationprogresses during ageing, peak F is close to
disappearing, while S’ precipitation is limited to heterogeneous nucleation on
dislocations and the corresponding peak E is already present.
Peak D must therefore be assigned to R precipitation as tentatively proposed by
Chester and Polmear (1981).
In the thermogram for the T7 temper the exothermal effects noticed previously
cannot be detected; only the dissolution peak C, whose position has again increased in
temperature (it is now positioned at about 250”C), and the large effect G are present.
This feature indicates that all the hardening phases have been formed during 190°C
ageing and they cannot precipitate during the subsequent calorimetric scan.
Moreover the evolution of the thermograms detected for the T4 temper and for the
samples aged at 190°C indicates that the phases which contribute to age hardening are
responsible for the exothermal effects B, D, E and F. These are the result of a
precipitation taking place during the calorimetric scan, and they are not present if the
precipitation has already occurred before the scan, that is during ageing at 190°C.
 480 S. Abis et al.

Fig. 14
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(4 (b)
T7 sample: (a)bright field showing Q, 0'and S' precipitates; (b)diffraction pattern obtained from
the (001) matrix zone axis.

Fig. 15

SADP taken from the (01 1 ) matrix zone axis of the T7 sample.

Figure 14(a)shows the presence of R, 0' and S' as can also be inferred from the
corresponding (Ool),, zone axis diffraction pattern reported in fig. 14(b). The
continuous streaks present in the corresponding (001 ), pattern relative to the sample
aged for 1 h are no longer clearly detectable. In that case they were associated with the
@"-phase whereas they have now been substituted by reflections typical of the
@'-phase.
 High temperature ageing of Al-Cu-Mg-Ag 48 1

Fig. 16
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Bright-field image of the T7 temper (two-beam condition; g =(200)).

Fig. 17

Diffraction pattern taken from the (1 11) matrix zone axis for the T7 temper.

Since the DSC trace shows that the 0” dissolution peak C has moved towards
higher temperatures, the disappearance of the streaks indicates that 0” particles are so
large that their structure is very close to a’,and therefore their dissolution temperature
is approaching the corresponding temperature for 0‘ precipitation.
The (01 l)A,pattern reported in fig. 15 is similar to the corresponding pattern taken
from the sample aged for 1 h. Nevertheless a new reflection can be detected in it
 482 S. Abis et al.

Fig. 18
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Bright-field image relative to the T7 temper; hexagonally shaped Q particles are visible :,;ether
with 0’and S’ precipitates.

is attributable to the @’-phase. The streaks along [1oo]A, detected for the previous
sample and typical of 0” are no longer present. The same conclusion reported above for
the (001)A, pattern can be drawn.
A bright-field image taken in two-beam conditions (g =(200))(fig. 16)shows both R
and 0’and/or 0”precipitates. The density of the latter appears to be decreased with
respect to the previously considered temper; this can be linked to a coarsening
phenomenon associated with a reversion of the smaller particles supplying copper
atoms also to the R-phase.
The diffraction pattern from (1 1 l)Al(fig. 17)can now be indexed on the basis of the
orthorhombic R lattice as reported in the literature (Muddle and Polmear 1989). R
particles exhibiting the typical hexagonal shape are now clearly visible (fig. 18).

0 5. CONCLUSIONS
Joint DSC and TEM analysis has been used to study the microstructural evolution
of the aluminium alloy A201 during ageing at 190°C after solution treatment,
quenching and room-temperature ageing. Several conclusions can be drawn as follows.
(1) At room temperature, two different kinds of phase appear: copper GPZs
typical of Al-Cu based alloys and another one, here named R’,which exhibits a
hexagonal structure with lattice parameters a = 0.507 nm and c = 0.692 nm.
This precipitate can be regarded as a slight modification of a phase belonging to
the Al-Cu-Mg system, due to a compositional difference probably linked to
the presence of silver atoms. R’ has been proposed to be an early precursor of
the well known R-phase.
(2) After ageing for a few minutes at 190°C,the GPZs disappear, and the 0” phase
can be detected. At the same time, small R precipitates nucleate while R’ still
remains present.
 High temperature ageing of Al-Cu-Mg-Ag 483

Table 2. Precipitation sequence of aluminium alloy 201 at 190°C.

Precipitates for the following alloy conditions

T4 Aged for 15min Aged for 60min Aged for 600min

GPZs 0'' 0"+ 0' 0'

R' R'+R R'+R R
S' S'
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(3) After ageing for 60min, the 0"particles are so large that the 0"+0'
transformation has already started, and a mixture of 0"and 0'is present. It
should be emphasized that DSC traces indicate that there is a continuous
evolution in the ON+@'process as indicated by the displacement of the 0"
dissolution peak, which approaches increasingly higher temperatures (and
therefore the 0' dissolution temperature) as the ageing time is increased. The
size of the R precipitates is now increased with respect to the previous temper
but the diffraction patterns indicate that the precursor still survives. Moreover
heterogeneous nucleation of S' on defects has started.
(4) In the T7 temper, after ageing for 10 h, only O', R and S' are present as already
reported in the literature. The whole precipitation sequence is described in
table 2.

ACKNOWLEDGEMENT
This work was performed for 'Progetto Finalizzato Materiali Speciali per
Tecnologie Avanzate' (CNR), under contract No. 83.00605.68.

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