Precipitation in AI-Cu-Mg-Ag

casting alloy
J. A. Taylor, B. A. Parker, and I. J. Polmear

220°C.4.6 - 8 For compositions that were studied which had

Castings made from AI-Cu-Mg-Ag alloys have a Cu: Mg ratios in wt.-% between 0·4: 1 and 2·1 : 1 (0'15: 1
high response to hardening in the artificially aged and 0·85 : 1 at.-%), silver promotes formation of a complex
condition. This effect is considered to arise because fcc T-phase (AI6(Cu, Ag)Mg4) rather than GPB(Cu, Mg)
silver changes the ageing process occurring in the zones and the orthorhombic phaseS (possibly S'), that
equivalent ternary AI-Cu-Mg alloy and promotes normally form during ageing.6 - 8 Silver also causes an
precipitation of thin plates of a monoclinic form of the increased response to age-hardening in a composition AI-
phase 8(CuAlz) on the {Ill} matrix planes. Replacing 2'5Cu-0'5Mg (Cu : Mg = 5 : 1wt-%, 1·9: 1 at.-%) in which
silver with cadmium also causes increased hardening, the microstructure of the aged ternary alloy usually contains
although the effect is less and arises from a refinement a mixture of those phases that form during ageing of both
in the size of precipitates formed in the existing ageing the AI-Cu and AI-Cu-Mg systems.9 However, in this case,
process. it has been found tl\at silver does not promote formation of
a T-phase; rather it causes thin plates of a monoclinic form
Paper No. MS 707. Manuscript received 27 April 1978; in final of the phase 8(CuAlz) to form on the {Ill} planes of the
form 9 June 1978. J. A. Taylor, BE, was, and B. A. Parker, BSc,
aluminium matrix with which it may be coherent.1O·11
ARSM, Die, PhD, and I. J. Polmear, BMetE, MSc, DEng, are in
the Department of Materials Engineering, Monash University, Normally 8 has a body-centred tetragonal structure and
Melbourne, Australia. forms on the {100} planes. The lattice dimensions of the.
monoclinic 8 unit cell have been determined by X-ray
diffraction to be a = b = 0·496 nm, C = 0·848 nm and
y = 120'6°.11
The Cu: Mg ratio in the AI-Cu-Mg-Ag casting alloys is
about 15: 1 wt-% (6'6: 1 at.-%) and it is possible that
hardening is also associated with formation of the same
monoclinic 8 phase. Thus the first aim of the present work
Castings made from AI-Cu-Mg-Ag alloys develop tensile was to test this hypothesis by investigating the effects of
properties on artificial ageing that are notably greater than 0'7% silver on precipitation in the basic ternary alloy AI-
those of other cast aluminium alloys and which, in fact, are 4·7Cu-0·27%Mg. The second part of the work involved a
comparable with properties normally expected from the study of the possible effects of cadmium on the same alloy
range of high-strength wrought alloys. Commercial AI-Cu- since trace amounts of this element are known to stimulate
Mg-Ag alloys are now available in the US (designated KO- precipitation of a fine dispersion of the partly coherent
1 or 201)1 and in France (designated Avior).z Each have tetragonal precipitate 8' in binary AI-Cu alloys. 12 •.13
basic compositions close to AI-4'7Cu-0'27Mg-0'7%Ag and
Avior has an additional 1'3% zinc. Castings prepared from
high-purity metals, and using premium-quality casting
techniques, are quoted as giving guaranteed properties of EXPERIMENTAL DETAILS
345 MNm-z yield strength and 415 MNm-z tensile The three alloys studied all nominally contained 4·7Cu-
strength, together with a minimum elongation of 5% if aged 0'27%Mg; one had the basic ternary composition and the
to the T6 temper (commonly 20 h at 155°C).1 Moreover, other two also contained 0'7% silver and 0'5% cadmium,
values as high as 480 MN m - Z yield strength and respectively. Although optical microscopy confirmed that
550 MN m -z tensile strength with 10% elongation have all the silver could be dissolved during subsequent solution-
been recorded. Accordingly the alloys are being considered treatment, the cadmium addition was well in excess of the
as replacements for forgings in applications in which they solid solubility which has a maximum of only 0·1% in binary
are cost effective. AI-Cd alloys.14
The high tensile properties arise because the alloys show a The alloys were melted in a graphite crucible using high-
marked response to age-hardening but very little has been purity materials, degassed with chlorine, and chill-cast in an
published concerning the mechanism of precipitation. Misra iron mould to give ingots 240 x 110 x 28 mm. No grain-
and Oswalt3 have attributed this response to the effect of refining elements were added. The actual compositions of
silver in stimulating the ageing process that normally causes the alloys are shown in Table I. The ingots were.
hardening in AI-Cu alloys, i.e. G P zones ~ 8" ~ 8'. homogenized for 24 h at 500°C and sectioned to provide
However, earlier work has shown that silver has little or no specimens for determining hardness/time (ageing) curves
effect on the artificially ~ged binary alloys.4.5 On the other and tensile properties, as well as for electron microscopy
hand, it has been found that a small amount ( ""0·1 at.-%) of and diffraction. Solution-treatment of these specimens was
silver does modify precipitation in a wide range of ternary carried out at 520°C after which they were cold-water-
AI-Cu-Mg alloys aged at temperatures between 120 and quenched and aged in oil baths at 130, 170, and 230°C.

478 Metal Science October 1978

 Tay/or et at. Precipitation in AI-Cu-Mg-Ag casting alloy 479

Table I Alloy compositions and properties

Composition, wt-% Cu
Mg
Ag
Cd

Temp.,oC

Peak hardness 130

170
230

Temp.,oC

Maximum tensile properties 170

230

170
230

RESULTSAND DISCUSSION quaternary alloys. At 230°C, all ageing curves had only one
Hardness/time curves at 130, 170, and 230°C are shown in stage.
Fig. 1. At 130°C, the alloys hardened in at least two stages Significant differences were recorded in the peak hardness
as the ageing curves each showed a distinct plateau as well values of the three alloys which increased in the order AI-
as a maximum value. Hardening occurred rapidly during Cu-Mg, AI-Cu-Mg-Cd, and AI-Cu-Mg-Ag at each of the
the first stage in both the quaternary alloys in a manner that three temperatures. Tensile properties determined for
is normally 'associated with the formation of G PB zones in a specimens aged to peak hardness at 170 and 230°C
wide range of ternary AI-Cu-Mg alloys.4,6-9,15 On the confirmed this result (Table I). Moreover, it is interesting to
other hand, initial hardening was more gradual with the note that the tensile properties recorded for the silver-
ternary alloy and was more characteristic of the GP(Cu) containing alloy aged at 170°C were equal to the guaranteed
zone formation that occurs in binary AI-Cu alloys. The values quoted for the commercial alloy KO-1 (201), even
hardness increment during the second stage of hardening of though the present material was not grain-refined.
the quaternary alloys was significantly greater than that The microstructures of the alloys were compared after
associated with the first stage (e.g. 54 HV compared with they had been aged for times corresponding to peak
30 HV) for the silver-containing alloy, whereas the reverse hardness at 170 and 230°C. For this purpose thin sections
was true with the ternary alloy (18 HV compared to 37 HV). were cut from heat-treated blocks and electropolished in
-:I:wo-stagehardening was again evident in the ternary Lenoir's solution at 70°C, using the window technique to
alloy aged at 170°C but appeared to be absent in the two produce foils for examination in a JEM 100C electron

Table II Analysis of microstructures

Alloy

AI-Cu-Mg 1. S (possibly S') coarse laths 1. Large laths of S

'" 600 x 50 x 50 nm
2. f)' as plates on {100} planes 2. f)' as plates'" 300 x 300 x 10 nm
'" 150 x 150 x 10 nm
3. Streaking in < 100) directions (f)"?) 3. Streaking in (100) directions

AI-Cu-Mg-Cd 1. S as laths '" 200 x 7 x 7 nm 1. S as coarse laths

'" 500-800 x 20 x 20 nm
2. f)' as plates on {100} planes 2. Small amount of f)' -phase
'" 100 x 100 x 10 nm
3. Streaking in <100) directions 3. Streaking in < 1(0) directions

AI-Cu-Mg-Ag 1. Hexagonal plates on {Ill} planes 1. Hexagonal plates on {Ill} planes

'" 200-400 nm in size and '" 400 nm in size 5-10 nm thick
2-:4 nm thick
2. Streaking in < 111) directions 2. Streaking in < 111) directions
and < 100) directions

Metal Science October 1978

480 Taylor et al. Precipitation in AI-Cu-Mg-Ag casting alloy

160 was approximately 0·9 nm and compared well with the value
of 0·848 nm for monoclinic 8,it is concluded that the phase
140 present. in the AI-Cu- Mg-Ag alloy is also the monoclinic
form of 8.
120
Electron diffraction patterns of all alloys aged at 170°C
showed streaking in the < 100) matrix directions which
could arise from the presence of one or both types of G P
100 zones, or from the thin plates or laths of the other
precipitates. The fact that the ternary alloy had a relatively
80 high plateau hardness compared to peak hardness suggests
x--x AI-Cu-Mg-Ag
that zone-hardening is significant and thus seems likely to
60 -- t:r-----6 Al -Cu-Mg -Cd
0-0 AI -Cu -Mg
be the main reason for the streaking in this case. However,
the absence of a first stage in the ageing curves suggests that,
although GP zones may be present, they do not make an
40
160
important contribution to hardening of the other alloys
aged at 170°C. Streaking in the < 111) directions in the AI-
Cu-Mg-Ag alloy probably arises from the very thin (2-
140
4 nm) plates of the monoclinic 8-precipitate.
0, If these conclusions are correct they have interesting
~ 120 implications with respect to the two quaternary alloys. This
follows because the silver-containing alloy has a lower
>
I 100 precipitate density than the alloy containing cadmium, and
yet shows a greater response to hardening. Accordingly, it
If)
If) seems that the thin plates of the monoclinic 8-phase are a
w 80 particularly potent source of hardening which, in the
z x
0
a:: 60
absence of evidence of coherency strains in the electron
« micrograph, probably arises because the precipitates lie on
I
the slip planes in the silver-containing alloy.
40 Ageing at 230°C still caused significant hardening in the
140 silver-containing alloy. The thin plates had increased in size
ageing temperature 230°C
and thickness but the general appearance of the micro-
120 structure was unchanged (Fig. 3(a)). On the other hand, the
density of precipitates was much reduced in the AI-Cu-Mg-
100 Cd alloy and the 8'-phase was largely replaced by the S-
phase (Fig. 3(b)). This indicates that the stability of the
monoclinic 8-precipitate in the AI-Cu-Mg-Ag alloy is
relatively high when compared with precipitates in other
aluminium alloys.
It remains now to consider the mechanism by which silver
induces formation of monoclinic 8. Such a mechanism must
be particularly effective because the activation energy
associated with nucleatIon of the closely similar 8(CuAI2)-
phase is relatively high, the monoclinic 8-phase is caused to
form on different matrix planes, and its morphology is
changed.
One possibility is that silver dissolves in the tetragonal 8-
phase and alters its lattice characteristics. This is unlikely,
however, because silver should also be effective in binary
AI-Cu alloys which is not the case. A second suggestion
microscope. Transmission electron micrographs are shown arises because Baba5 has proposed that silver atoms cluster
in Figs. 2 and 3 and additional information was obtained by preferentially along {111} planes of the aluminium lattice
means of electron diffraction patterns prepared from the which may be significant because the new precipitate does
same foils. Results are summarized in Table II. form on these planes. If this segregation does occur then it
For alloys aged at 170°C silver and cadmium both changed could be postulated that the silver atoms, in some way,
the appearance of the precipitate that normally forms in the stimulate nucleation and growth of the monoclinic form of 8
ternary composition. Cadmium greatly refined the size and along these planes. Once again, it is necessary to account for
increased the density of 8'-plates, as occurs when this the fact that silver is ineffective in binary AI-Cu alloys, and
element is added to binary AI-Cu alloys (Fig. 2(a)-(c)). It a possible explanation is that it is silver-magnesium
also appeared to stimulate formation of this phase in complexes which actually influence the nucleation and
preference to the S-phase. The effect of silver was even more growth of this phase. In this regard there is strong evidence
dramatic as it changed both the appearance of the that all the effects of silver in aged aluminium alloys arise
precipitate and the planes on which it formed. As shown in initially from a preferred interaction between these
Fig. 2(d) thin hexagonal-shaped plates were formed on the elements.4 The precise mechanism for such a nucleation
{111} matrix· planes and no clear evidence was found for the process is uncertain but it is interesting to note that
presence of either 8' or S. The precipitate has the same magnesium and silver do form a stable intermetal1ic
appearance as the phase identified by Auld as a monoclinic compound Mg3Ag which is hexagonal with a = 0·493 nm.16
form of 8. Moreover, since electron diffraction measure- This is close to the value of a = 0·496 nm determined by
ments showed that the lattice dimension in the c direction Auld for monoclinic 8.11 Moreover, the fact that Mg3Ag has

Metal Science October 1978

 Taylor et al. Precipitation in AI-Cu-Mg-Ag casting alloy 481

~) ~)

(c) (d)
2 Transmission electron mi-:rographs for the three alloys aged to peak hardness at 170°C.

a hexagonal crystal structure may also be significant as the aluminium matrix. This phase, which is believed to be a
monoclinic (j forms as well-defined hexagonal plates (Fig. monoclinic form of the precipitate (j(CuAI2), appears to be
2(d». Thus it is tempting to speculate that magnesium and particularly efficient at stimulating hardening, possibly
silver atoms segregate to the {Ill} matrix planes to form because it forms on the slip planes. It has a relatively high
very small particles or nuclei of Mg3Ag which, in turn, serve stability over a wide temperature range.
both to nucleate monoclinic (j and dictate its morphology. 3. The mechanism by which silver promotes precipitation
of monoclinic (j is uncertain but· one suggestion is that its
nucleation and growth may be controlled through prior
CONCLUSIONS formation of the compound Mg3Ag on the {Ill} matrix
1. The high tensile properties developed in artificially planes.
aged AI-Cu-Mg-Ag casting alloys arise because silver 4. Cadmium also modifies precipitation in the equivalent
changes the precipitation process that normally occurs in ternary AI-Cu- Mg alloy, and causes increased age-
the equivalent ternary AI-Cu-Mg alloy. hardening at some temperatures by promoting precipitation
2. Silver promotes formation of thin hexagonal-shaped of a finer dispersion of the phase (j' as also occurs when this
plates of a phase that precipitates on the {Ill} planes of element is added to binary AI-Cu alloys.

(a) (b)
3 Transmission electron micrographs for the AI-Cu-Mg-Ag and AI-Cu-Mg-Cd alloys aged to peak hardness at
230°C.

Metal Science October 1978

482 Taylor et al. Precipitation in AI-Cu-Mg-Ag casting alloy

ACKNOWLEDGEMENT 6. J. H. AULD, J. T. VIETZ, and I. J. POLMEAR: 1966,209, 703.

Nature,
This work forms part of an investigation of the effects of 7. J. T. VIETZ and I. J. POLMEAR: J. /nst. Met., 1966,94, 410.
minor elements additions in aluminium alloys and is 8. N. SEN and D. R. F. WEST: 'The mechanism of phase
transformations in crystalline solids', p. 49. 1969: London
supported by the Australian Research Grants Committee.
(Inst. MeL).
9. J. M. SILCOCK: J. /nst. Met., 1960-61,89, 203.
10. J. H. AULD and J. T. VIETZ: Ref. 8, p. 77.
REFERENCES 11. J. H. AULD: Acta Cryst., 1972, 28A, 98.
1. A. J. ILER: Met. Progr., 1969 (Jan.), p. 57. 12. I. J. POLMEAR and H. K. HARDY: J. /nst. Met., 1952-3,81, 427.
2. M. O. SPIEDEL: Proc. 6th InL Conf. 'Light metals', Leoben, 13. J. M. SILCOCK, T. J. HEAL, and H. K. HARDY: ibid., 1953-4,82, 239.
Austria, 1975, p. 67. 14. H. K. HARDY: ibid., 1951-2, 80, 431.
3. M. S. MISRA and K. J. OSWALT: Met. Eng. Q., 1976,16, 39. 15. H. K.HARDY: ibid., 1954-5,83, 17.
4. I. J. POLMEAR: Trans. Metall. Soc. A/ME, 1964, 1331. 16. 'Metals reference book', 4th edn. (ed. C. J. Smithells). vol. 1, p.
5. Y. BABA: Trans. J. /nst. Met., 1965,10, 188. 161. 1967: London (Butt~rworths).

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