Scripta M E T A L L U R G I C A Vol. 22, pp.

927-932, 1988 Pergamon Press plc

Printed in the U.S.A. All rights reserved

VIEWPOINT SET No. 13

ON THE STRUCTURES OF GUINIER-PRESTON ZONES IN AL-CU ALLOYS

INTRODUCTORY PAPER

V. Gerold
Max-Planck-lnstitut fur Metallforschung, I n s t i t u t fur Werkstoffwissenschaften,
Stuttgart, and I n s t i t u t fur Metallkunde, Universit~t Stuttgart
D-7000 Stuttgart 1, FRG
(Received March 17, 1988)
(Revised April 27, 1988)

Introduction

Since the early eighties the interest in the atomic structure of the two kinds of Guinier-
Preston zones (G.P. zones) I and I I in Al-Cu alloys has revived, and many papers on this subject
have been published since then. The reason for this regained interest in the old problem is the
experimental evidence of new structures by the application of new techniques such as f i e l d ion
microscopy (FIM) or high resolution transmission electron microscopy (HREM). The results of the
refined analysis of diffuse X-ray diffraction from single crystals have also added to this
interest.

The f i r s t evidence of these zones has been found in the late t h i r t i e s , independently by Guinier
(1) and by Preston (2), who applied different X-ray techniques. These zones are the f i r s t stages
of phase separation in the supersaturated solid solution of AI-Cu. Their atomic structures have
been established in the f i f t i e s , again by X-ray techniques. At room temperature mainly G.P.I
zones develop which give rise to intensity streaks passing through the Bragg peaks in the direc-
tions of the cubic axes of the reciprocal l a t t i c e . Fromtheir asymmetric appearance i t was con-
cluded that each zone consists of a monolayer of Cu atoms on a {200} l a t t i c e plane surrounded by
a far-reaching elastic distortion f i e l d due to the smaller size of the Cu atoms comparedto the
Al atoms (3). The l a t t e r conclusions were drawn from the strong asymmetric intensity increase
found on both sides of the Bragg peaks (so-called Huang scattering). I t could be estimated that
the l a t t i c e spacing between the Cu and the nearest Al layer has decreased by the order of 10 %.

At elevated temperatures (100 to 180C) the G.P.II zones appear which show diffuse superstruc-
ture spots superimposed on the streaks of the G.P.I zones. By an alternating heat treatment bet-
ween 198 and 493 K (125 and 220C) i t could be shown that the streaks disappear after short
annealings at 493 K, but not the diffuse spots of the G.P.II zones. The l a t t e r disappeared only
at higher temperatures, around 533 K (260C). After prolonged aging at 198 K the streaks reap-
pear and gradually decrease in intensity while the diffuse spots of G.P.II zones develop (3).
The atomic structure of these zones could not be clearly described, however. The proposed models
agree in a periodic arrangement of four { 2 0 0 } layers where one layer consists mainly of Cu
atoms. The other layers were assumed to be either pure Al (3) or to have a certain content of Cu
atoms (4,5). The average l a t t i c e spacing in the tetragonal c direction is about 2 to 3 % smaller
compared to that in the solid solution matrix. Again, strong elastic l a t t i c e distortions occur
mainly in the direction perpendicular to the layers. These two types of zones I and I I w i l l be
termed classical and compared to the new structures observed more recently.

The aim of the present Viewpoint Set is to review the present state of the art of this topic
which is s t i l l controversal regarding the details of interpretation and the v a l i d i t y of sub-
sequent conclusions. This introductory paper summarizes the results reported in recent years by
various authors and w i l l introduce the other papers of this Set. Only those papers w i l l be re-
viewed which use diffraction techniques of X-rays or neutrons or imaging techniques such as FIM

927
928 G-P ZONES Vol. 22, No. 7

or HREM. Papers describing the results of other investigation techniques as extended X-ray ab-
sorption fine structure (EXAFS) w i l l not be referred since those results seem to be less re-
l i a b l e than the others.

On the New Structure Types of G.P.I Zones

During the last seven years many papers have appeared in the l i t e r a t u r e questioning the classi-
cal results on the structure of the zones which have been sketched above. Thus, for the G.P.I
zones variants of the single layer zone have been found which consist of two or more adjacent
layers of Cu atoms on (200) planes of the l a t t i c e . They could be observed by FIM techniques and
by HREM, and they followed from the analysis of diffuse X-ray diffraction.

In an early paper by Dorignac et al. (6) there was already a hint that there might exist also
double layers of Cu atoms besides the single-layered G.P.I zones. This was concluded as a p r e l i -
minary result from an electron microscopic l a t t i c e image of a sample aged for 50 h at 100C.
However, the more convincing results were given by Auvrey et al. (7) who measured and analyzed
the diffuse Laue scattering of X-rays from a single crystal of an Al-Cu alloy aged for more than
12 years at ambient temperature.

In their analysis of the diffracted intensity the authors separated the intensity term ISR0 con-
taining only the information on short range order (SRO) from those terms containing the informa-
tion on l a t t i c e distortions. They used the improved method by Georgopoulosand Cohen (8) which
takes into account the variation of the atomic scattering amplitudes with d i f f r a c t i o n angle
(more exactly, the variation of their ratios as f A l / ! f c v - f A l ) which were assumed to be constant
in the older Borie-Sparks method). From this analysls the authors claimed that a r e l a t i v e l y
large amount of G.P.I zones (about 20 to 25 %) consists of multilayer zones where two to five
adjacent layers are enriched by Cu atoms. These findings were reconfirmed by the sameresearch
group, by Matsubara and Cohen (9), using synchrotron radiation. They also found a much less pro-
nounced distortion f i e l d around the zones in contrast to the classical model (3). The authors
draw their conclusions without measuring the intensity distribution close to the Bragg spots.

In his present contribution to this Viewpoint Set, Cohen (10) reconfirms the results of his
research group on AI-Cu by similar results on the G.P. zone state in Cu-Be. He stresses again
the importance of the correct value for the integrated intensity of ISR0 which he gets in a l l
his analyses. This is taken as a direct proof for the correctness of his results: the existence
of a large amount of multilayer zones in Al-Cu and in Cu-Be alloys.

These t o t a l l y new results more or less agreed with the findings of other research groups who
were involved with different investigation methods to study the microstructure of such aggre-
gates. In a j o i n t e f f o r t three different Japanese groups investigated the same sample used by
Auvray et al. and they reconfirmed the new results by FIM, HREMand small angle scattering (SAS)
of X~rays (11). For all three investigation methods evidence was given for the existence of a
considerable amount of multilayer zones besides the monolayer G.P.I zones.

These results were in agreement with e a r l i e r experiments by the same Japanesegroups. For
example, Hirano and his co-workers, using the FIM technique, found evidence for multilayer G.P.I
zones after aging at 403 K (130C) (12). These layers of Cu atoms contain many terraces, ledges
and vacancies. The existence of multilayers was reconfirmed by later experiments(13 to 15)
where the image of the sample t i p was followed into the third dimension by careful step-wise
evaporation of surface monolayers of the sample t i p . The number of multilayer zones was roughly
estimated to be less than the number of monolayer G.P.I zones (14). Since the stable solid sol-
ution at high temperatures consists of solute clusters of two and three dimensions (16) these
clusters were thought to be the reason for the nucleation of single and multilayer zones (14). A
careful atom probe analysis (13,15) gave information of the average Cu content of the multilayer
zones which was found to be between25 and 45 % which differs markedly from the results by
Auvrey et al. (7) and Matsubara and Cohen (9) who found values close to 100 %. For the depleted
matrix a Cu content of 0.75 % was given (13,15). These results are confirmed again by Hirano
(17) in his Viewpoint paper

The existence of multilayer zones was also reported by Sato et al. (18) who used HREMin their
investigation in a t i l t e d beam set-up comparable to that used by Ajika et al. as described later
on. They estimated the amount of such zones to be only in a 10 to 20 % range, however. In their
present contribution to this Viewpoint Set, Sato and Takahashi (19) examinequantitatively the
Vol. 22, No. 7 G-P ZONES 929

frequency distribution of the different types of G.P.I zones and conclude that 86.3 % of the
zones are classical G.P.I zones after room temperature aging. The remaining 13.7 % were found to
be two- and three-layer zones and also more complex ones containing an Al layer between two Cu
layers.

On the new Structure Types of G.P.II Zones

While there is someagreement on the new structures of G.P.I zones, various structures for the
new G.P.II zones are reported. Fromtheir investigation of diffuse diffraction of synchrotron
radiation from a single crystal aged for 133 h at 383 K (110C) Matsubara and Cohen (20) con-
cluded that there is no different structure for these zones. They are thought to be a coarsened
stage of the multilayer G.P.I zones and consist mainly of f i v e adjacent Cu layers with a rough
surface. The superstructure spots found in X-ray d i f f r a c t i o n are thought not to be caused by an
internally ordered structure but by an interference effect due to the small thickness of the
zones. This result was substantiated by a recent investigation of the precipitates developing
after a direct quench to the aging temperature of 463 K (190C) by TEM (21). This temperature is
between the two s o l u b i l i t y limits in the metastable phase diagram reported for G.P.I (180C) and
G.P.II zones (220C). I f there exists a separate phase G.P.II, i t should nucleate as the f i r s t
phase in this temperature range. The experiments reveal, however, that only the next stable
phase, 8', nucleates. Therefore, i t was concluded that the G.P.II zones are a coarsened species
of G.P.I zones. This point of view is given again by Cohen (10) in his present contribution to
this Viewpoint Set.

Quite different types of new structures for the G.P.II zones have been found by other methods,
however. For example, Hirano and his co-workers (14,15) reported that they could find ordered
structures of the classical G.P.II zones by FIM, consisting of two Cu-rich layers separated by
two or three layers of lower Cu content. Fromtheir atom probe analysis they found a Cu content
of only 30 to 50 % for the Cu-rich layers. For the adjacent 5 to 7 matrix layers a Cu content
was reported which was substantially higher than that of the depleted matrix (0.75%). These re-
sults are presented again (17) in the present Viewpoint Set. From their HREMexperiments Sato et
al. (18) give evidence for zones consisting of two Cu layers separated by a single Al layer and
of other more complex structure types. This result is stated again in the contribution to this
Viewpoint Set by Sato and Takahashi (19) investigated quantitatively the frequency distribution
of the different types of zones occurring during aging at 423 K (150C).

Arguments Against the New Structure Types of G.P.I Zones

Not a l l investigators agree with these new results. For the case of G.P.I zones, for example, in
a careful FIM study, Wada, Kita and Mori (22) concluded that only monolayer G.P.I zones are pre-
sent in a sample aged for 16 h at 130C. They emphasize that clear images of zones can only be
found i f they appearnear the center of atomically smooth and reasonably large low-index top
planes of the sample t i p . They studied about ten G.P.I zones in this way without finding a
single multilayer zone. This result differs t o t a l l y from that of Hono et al. (14) who stated
that a substantial amount of zones but less than 50 % are multilayers. Unfortunately, the ex-
periments by Wada et al. were not continued, thus the existence of multilayers cannot be ex-
cluded because of the limited number of investigated zones.

In t h e i r HREMstudies Yoshida and his co-workers investigated very thin f o i l s of an Al-Cu alloy
aged for 3 h at 413 K (140C) by l a t t i c e imaging. In one of their papers Ajika et al. (23) made
a careful analysis comparing the experimental results with contrast calculations. They used a
t i l t e d beam illumination where the optical axis of the microscope was adjusted to the center of
the four reflections (000), (200), (220) and (020). In that case the diffuse i n t e n s i t y streaks
caused by the G.P. zoneswere in an angular range where the phase contrast transfer function of
the microscope had a constant value. They also used a f o i l thickness of about 12 nm which pro-
duced the same phase s h i f t for a l l four beams used for the image formation. They could explain
a l l contrast patterns by the assumption that the G.P.I zones consisted of a single layer of Cu
atoms surrounded by a far-reaching strain f i e l d . Again, only very few aggregates were investi-
gated this way, and no general conclusions can be drawn. The present contribution by Yoshida
(24) to this Viewpoint Set reviews his former results.

The main controversary has arisen on the results of diffuse X-ray scattering by Auvrey et al.
(7) and Matsubara and Cohen (9). In both cases the method of Georgopoulosand Cohen (8) was
used. This method has to approximatethe influence of l a t t i c e distortions since otherwise a
930 G-P ZONES Vol. 22, No. 7

separation of the term ISR0 containing only the information of the atomic distribution is not
possible. The distortion parameters occur in exponential expressions which are expandedin a
power series up to the second order. This approximation is only sufficient i f the distortions
are not too large, and their condition may not be f u l f i l l e d in the present case. By a simple
one-dimensional model calculation i t was shown that indeed an incorrect ISR0 results on the
basis of t h e i r approximation i f the l a t t i c e distortion around a G.P.I zone (25) is l a r g e as
generally assumed. These argumentswere not accepted (26) mainly because both original papers
(7,9) gave a correct integrated intensity of the ISR0 term which should not be the case i f there
was an incorrect term separation. From these findings i t was concluded that the errors made for
ISR0 must be very small.

Since the questioned diffuse diffraction experimentswere undertaken under reflection condi-
tions, i . e . , outside the f i r s t B r i l l o u i n zone of the reciprocal l a t t i c e , Bubeck and Gerold (27)
investigated by transmission techniques the diffracted intensity inside this zone in order to
v e r i f y the results by Cohenand his co-workers. As the contribution of the l a t t i c e distortion
terms is minimum in this region i t could be expected that the diffracted intensity in this
region is more sensitive to the contribution of multilayers than in other regions. They extended
their investigation by measuring the intensity distribution along <hO0> under reflection condi-
tions from h = 0.8 to h = 5 (measured in units of the reciprocal l a t t i c e constant l / a ) . Their
experimental results could be explained by assuming only monolayer G.P.I zones. A difference
between experiment and model calculation occurred only at large angles beyond the (400) spot and
may be caused by insufficient corrections for the thermal vibrations. According to the authors,
an amount of 2 % three-layer zones should alter the intensity distribution in the f i r s t
B r i l l o u i n zone which was not observed experimentally. Since the experiments were compared only
with model calculations no clear proof could be given for or against the new structures. The
present contribution by Gerold and Bubeck (28) to this Viewpoint Set describes a l l the results
of t h e i r experiments in the low-angle range.

From the fact that the distortion terms are minimum inside the f i r s t B r i l l o u i n zone i t can be
suggested that the inclusion of this region may considerably improve the accuracy of both term
separation methods (by Borie and Sparks and by Georgopoulos and Cohen). This improvementwas
shown by a one-dimensional analysis using the calculated intensity distribution from a single
layer G.P.I zone model surrounded by a large distortion f i e l d (29). For both separation methods
i t was found that a correct ISR0 term could be separated only in such cases where the intensity
distribution from the f i r s t B r i l l o u i n zonewas included. In a l l other cases erroneous results
were obtained. In that case the integrated intensity of ISR0 was always larger compared to that
of the correct ISR0 term. For smaller distortion f i e l d s , however, the inclusion of the data from
t h e f i r s t B r i l l o u i n zone was no longer necessary. In a reply to these findings (30) the use-
fulness of the suggested extension of the experiments to lower diffraction angles was questioned
since a different type of experimental set-up would be needed for X-rays which might introduce
additional inaccuracies in adapting the data.

The importance of the inclusion of the f i r s t B r i l l o u i n zone to the term separation methods has
been experimentally investigated very recently by Kostorz and his co-workers. Part of their re-
sults can be found as a contribution to this Viewpoint Set (31). Froman Al-Cu single crystal
aged for 60 min at 353 K (80C) the authors measuredneutron diffraction along <hO0> in the
range 0.2 ~ h ~ 6.9 and applied the Borie-Sparks method (the atomic scattering amplitudes are
v i r t u a l l y angle-independent in this case) for various h-ranges. They clearly show that con-
sistent results can only be obtained i f the f i r s t B r i l l o u i n zone is included in the analysis as
has been suggested before by model calculations (29). The consistency of the results is improved
by the inclusion of a third-order term to the analysis. For the correct ISO an angle-indepen-.
dent constant value was obtained which is typical only for monolayer zones. ~rom thls result the
authors conclude that a larger fraction of G.P.I zones than given in Refs. (?,9) must be single-
layered.

Arguments Against the New Structure Types of G.P.II Zones

For the new structure types of G.P.II zones there is at f i r s t a general disagreement whether
these zones simply are a coarsened product of multilayered G.P.I zones (10,19,21) or whether
they have a different structure with Al-rich layers between the Cu-rich layers (13-15,18,19).
Vol. 22, No. 7 G-P ZONES 931

The experimental result by Koo et al. (21) that G.P.II zones do not form after a direct quench
to the aging temperature of 463 K (190C) is certainly a proof that these zones are an aging
product of G.P.I zones. This must not mean, however, that they are a coarsened state of the
multilayer zones. In the classical point of view, the G.P.II zones have nucleation problems
which they can only overcome i f ( i ) G.P.I zones are present as nucleation sites and i f ( i i ) the
Cu content of the depleted matrix is s t i l l above a c r i t i c a l value (32). After they have nuc-
leated as classical G.P.II zones they are thermodynamically more stable t h a n G.P.I zones and,
therefore, they have a higher reversion temperature than the l a t t e r . This point of view is com-
patible with the result of Koo et al. (21).

The l a t t i c e imaging techniques by FIM and HREMclearly reveal G.P.II zones having Al-rich layers
between two Cu layers. The frequency distribution during aging at 423 K (150C) shows the domi-
nance of the classical zones while other types seem to increase in frequency with increasing
aging time (19), an increase when the f i r s t precipitates of the next stable phase (8') appear.
Further experiments are needed to substantiate these findings.

Conclusions

As this review has shown, quite different opinions exist on the occurrence of new structures
besides the classical types of G.P.I and G.P,II zones. For further progress, someagreement on
the results of an individual experimental method, such as diffuse scattering, is needed. I t is
suggested that the best chances for further c l a r i f i c a t i o n exist for the G.P.I zones which occur
during aging at and below 373 K (100C). At f i r s t , there is a need to come to an agreement on
the limits for the application of the term separation methods for diffuse X-ray or neutron scat-
tering in order to get r e l i a b l e results for ISRO. The recent results by Kostorz and his co-
workers (31) together with the theoretical considerations by Gerold and Bubeck (29) seem to show
a method to proceed in further investigations.

As a second step, a quantitative agreement between the different experimental techniques should
be reached. In spite of the fact that some agreementalready exists (11), new efforts are
necessary since there remain differences in d e t a i l . In addition, the recent results by Kostorz
and his group do not f i t into this picture.

For HREMexperiments a severe draw-back seems to be the necessity to use a tilted-beam method as
mentioned above. The non-axial illumination leads to an additional black-white contrast where
the l a t t i c e image is darkened on one side of a zone and brightened on the other similar to the
d i f f r a c t i o n contrast from G.P.II zones in conventional TEM micrographs ( 3 3 , 34). This makes a
quantitative analyisis of the zone structure more d i f f i c u l t . An improvementcertainly would be
reached by using imaging conditions with axial illumination. For this purpose, however, a better
resolution of the microscope is required. The new generation of high resolution microscopes
operating at a voltage of 300/400 kV may improve the situation (33).

Acknowledgement

My thanks are due to Prof. G. Kostorz and Dr. S. Mader for many helpful discussions and sugges-
tions.

References

1. A. Guinier, Nature 142, 568 (1938).

2. G.D. Preston, Nature 142, 570 (1938).
3. V. Gerold, Z. Metallkde. 45, 593 and 599 (1954).
4. A. Guinier, Acta Cryst. 5, 121 (1952).
5. J.M. Silcock, T.J. Heal and H.K. Hardy, J. Inst. Met. 82, 239 (1953/54).
6. D. Dorignac, M.C. Casanove, R. Jagut and B. Jouffrey, Electron Microscopy 1980, Vol.4, pp.
174.
7. X. Auvray, P. Georgopoulosand J.B. Cohen, Acta metall. 29, 1061 (1981).
8. P. Georgopoulosand J.B. Cohen, J. Phys. (Paris) Colloq. C17, 191 (1977).
9. E. Matsubara and J.B. Cohen, Acta metall. 33, 1945 (1985).
10. J.B. Cohen, this Viewpoint Set.
11. K. Osamura, Y. Murakami, T. Sato, T. Takahashi, T. Abe and K.-I. Hirano, Acta metall. 31,
1669 (1983).
12. T. Abe, K.Miyazaki and K.-I.Hirano, Acta metall. 30, 357 (1982).
932 G-P ZONES Vol. 22, No. 7

13. K. Hono, T. Hashizume, Y. Hasegawa, K. Hirano and T. Sakurai, Scripta metall. 20, 487
(1986).
14. K. Hono, T. Satoh and K. Hirano, P h i l . Mag. A 53, 495 (1986).
15. K. Hirano, Materials Science Forum 13, 215 (1987).
16. E. Matsubara and J.B. Cohen, Acta metall. 31, 2129 (1983).
17. K. Hirano, this Viewpoint Set.
18. T. Sato, Y. Kojima and T. Takahashi, Trans. Japan Inst. Met. 23, 461 (1982).
19. T. Sato and T. Takahashi, this Viewpoint Set.
20. E. Matsubara and J.B. Cohen, Acta metall. 33, 1957 (1985).
21. Y.M. Koo, M.E. Wall, L.E. Tanner and J.B. Cohen, Scripta metall. 21, 817 (1987).
22. M. Wada M., H. Kita and T. Mori, Acta metall., 33, 1631 (1985).
23. N. Ajika, H. Endoh, H. Hashimoto, M. Tomita and H. Yoshida, Phil. Mag. A 51, 729 (1985).
24 H. Yoshida, this Viewpoint Set.
25. V. Gerold and E. Bubeck, Scripta metall. 16, 1101 (1982).
26. J.B. Cohen and P. Georgopolous, Scripta metall. 19, 1107 (1082).
27. E. Bubeck and V. Gerold, Proc. 5th Riso Int. Symp.on Metallurgy and Materials Science, Riso
National Laboratory, Roskilde, Denmark, pp. 219 (1984).
2B. V. Gerold and E. Bubeck, this Viewpoint Set.
29. E. Bubeck and V. Gerold, J. Appl. Crystallogr. 19, 164 (1986).
30. J.B. Cohen, J. Appl. Crystallogr., 19, 491 (1986).
31. P.P. MUller, B. Sch~nfeld, G. Kostorz and W. BUhrer, this Viewpoint Set.
32. R. Baur, Z. Metallkde. 57, 368 (1966).
33. W. Mader, private communication.
34. M. v. Heimendahl and G. Wassermann, Z. Metallkde., 54, 385 (1963).