Scripta METALLURGICA Vol. 22, pp.

947-951, 1988 Pergamon Press plc

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

VIEWPOINT SET No. 13

SOMEASPECTS ON THE STRUCTUREOF GUINIER-PRESTON ZONES IN AI-Cu ALLOYS

BASED ON HIGH RESOLUTION ELECTRONMICROSCOPEOBSERVATIONS

H. Yoshida
Research Reactor Institute, Kyoto University,
Kumatori-cho, Osaka 590-04, Japan
(Received March 17, 1988)
(Revised April 27, 1988)

Introduction

Since the discovery of G.P. zones in Al-Cu alloys by Guinier (1) and Preston (2) in 1938,
the structure of these zones has been studied by many investigators and i t has becomean inter-
esting research subject in the f i e l d s of metallurgy and crystalography. Recent progress of
experimental techniques and equipments which allow optical imaging with high resolution lead us
to have more detailed information and to discuss the structure of G.P. zones on an atomic scale.
High resolution electron microscopy, as one of the most powerful techniques, has already given
atomic resolution images of crystals containing G.P. zones which include important information
about the atomic arrangements around G.P. zones in Al-Cu alloys (3-8). In this paper the essence
of our previous observations on an AI-3.9 wt.% Cu (1.74 at.% Cu) alloy using the weak-beamand
the multi-beam techniques are reviewed, discussed and comparedwith the structure models.

Structure of G.P.(1) Zones

An example for atomic resolution of an electron microscopic image of G.P. zones is shown in
Fig. 1 for the [001] oriented crystal agedfor 10.8 ks at 413 K followed by 2146.4 ks at room
temperature. The multi-beam images were obtained at various defocus values when the optical axis
was set on the center direction between the primary beam and the (200), (020) and (220) reflec-
tions. Under these optimum conditions clear images of l a t t i c e s are obtained which are distorted
by G.P. zones (9). In Fig. 1, the bright dots have been interpreted as images of rows of Al
atoms positioned in the [001] direction normal to the f o i l plane in a thin section of the
crystal (4,5). The arrays of dotted images with stronger brightness indicated by A, C, D and E
correspond to planes of Cu atoms of G.P. I zones lying on the (200) and (020) planes parallel to
the incident electron beam. The brighter dotted-images surrounded by dark contrast on either
side of the arrays were interpreted by contrast calculations based on the dynamic diffraction
theory. The model consists of a monolayer of Cu atoms which induces displacements of the sur-
rounding Al l a t t i c e atoms (5,9). I t is based on the same assumption as in a previous paper (10),
namely that the Cu layer behaves as a dislocation loop with a low Burgers vector which is
responsible for the distortion f i e l d in the Al l a t t i c e . Its magnitude is f i t t e d to match the
experimental observations. For the contrast calculation by the multi-slice method, however, the
atomic displacement at the model is assumed to be independent on the z direction. The model is
good enough to explain the multi-beam images of G.P.(1) zones.

From the appearanceof the l a t t i c e image i t can be concluded that there exists a far-
reaching displacement f i e l d in the v i c i n i t y of the Cu layer. Sometimesi t is influenced by
strain f i e l d s of other zones. For example, the displacement f i e l d continues from zone A to zone
E (8). Sometimes, an asymmetric displacement f i e l d was also observed as in zone D, while zone C
shows a symmetric f i e l d (8). The l a t t e r seems to be the standard structure (11). At positions F
and G the investigation of imageswith other defocus values led to the conclusion that these
images consist of the overlap of two G.P.I zones which have formed near the top or bottom in the
f o i l on different (200) planes which have a distance of two (200) layers. Such image overlapping
of two G.P.(1) zones sometimes appears when the f o i l is r e l a t i v e l y thick. There is no reasonable
image of a G.P.(I) zone showing multiple Cu layers (n-layers).

947
948 STRUCTURE OF G-P ZONES Vol. 22, No. 7

FIG. 1. Atomic resolution electron microscope image of Al-3.97wt%Cu alloy containing G.P.
zones. A, C, D and E indicate mono-layer G.P.(1) zones. B, M and N indicates double-
layer G . P . ( I I ) zones. F and G see text.

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otoms (~ ;~"
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FIG. 2. Model of GP.(1) zone used for interpretation of image contrast calculation.
Vol. 22, No. 7 S T R U C T U R E OF G-P ZONES 949

The model of a G.P.(1) zone (Fig. 2) used in this paper contains larger atomic displace-
ments and a wider displacement f i e l d than the model suggested by Gerold (12}. The top and bottom
numbers in the spheres represent the atomic displacement in the y and x directions, respective-
ly, given in units of ao/lO0 where ao is the l a t t i c e parameter (10). This structure suggests
that the effective atomic size of Cu atoms in the zone is s l i g h t l y smaller than the regular size
of Cu, which might be caused by an electronic structure producing two-dimensional Cu-Cu bonds in
the Al l a t t i c e . This may also be the reason for the formation of the monolayer structure of Cu
atoms avoiding multiple layers and a three-dimensional arrangement. There seem to be no argu-
ments for the existence of multi-layer zones of Cu atoms after low temperature aging. As the
model in Fig. 2 shows there exists a l a t t i c e compression in the y direction in the Al layer
adjacent to the end of the Cu layer. In these areas there may also be the sites for vacancies
which enhance the diffusion of Cu atoms from the matrix to the border of the Cu layer (7). When
after reversion for 60 s at 448 K the AI-3.g?wt%Cu alloy was aged for 5184 ks at room tempera-
ture small mono-layerG.P.(I) zones were formed with a high density, while after flash-annealing
for 60 s at 403 K an aging for 8900 ks at room temperature leads to a low density of G.P.(1)
zones with a large average diameter (13.5 nm). This size is much bigger than that formed during
the usual aging at temperatures between 383 and 413 K (11). All these facts suggest the mono-
layer of Cu atoms as the standard structure for G.P.(1) zones rather than a multiple layer
structure. For higher aging temperaturesthere may exist p o s s i b i l i t i e s for forming multi-layer
structures.

Structure of G.P.(II) Zones

In electron microscopic observations using the weak-beam and the multi-beam methods,
G.P.(1) and ( I I ) zones have been commonly observed to coexist in the early stages of aging in
Al-Cu alloys (3,4). For example, G.P.(II) zones are also seen in Fig. 1. There are the images of
double-layers of Cu atoms as indicated by M and N. The two Cu layers are separated by two and
three Al layers for the image M and N, respectively. The image N shows the familar atomic ar-
rangement with the standard structure of G.P.(II) zone (10,11) which consists of double-layers
of Cu atoms separated by three (020) planes. The image M shows a deviation from this standard
structure, where the atomic arrangement corresponds more to a layer of the intermediate 8' phase
having the thickness of half a l a t t i c e constant in the c direction. The complicated image B in
Fig. 1 can be roughly interpreted as a double-layer structure of G.P.(II) zone type with addi-
tional shear displacements as i t is found by contrast calculations (5,9). Both models of the
G.P.(II) zone with or without a shear displacementwere constructed in such a way that two
layers of Cu atoms were separated by three Al layers giving similar atomic displacements of the
surrounding Al l a t t i c e as in the model of the G.P.(1) zone (9).

When the size of G.P. zones was measured from weak-beammicrographs, the size distributions
of G.P.(1) and ( I I ) zones could be deduced as shown in Figs. 3 (a) and (b) for samples aged for
149.4 ks at 408 K and for 864 ks at 413 K, respectively (11). The shaded areas correspond to
G.P.(II) zones, and the others are G.P.(1) zones (index 1). The double-layer (dotted areas,
index 2) and multi-layer G.P.(II) zones (indices 3 to 10) are larger in the average size than
the G.P.(1) zones, but the size distributions overlap each other. In the growth process of the
zones the extra Cu atoms supplied near the edge of the f i r s t layer may form a nuclei there for
the second layer of Cu atoms. From Fig. 3 (a) i t is suggested that the probability to nucleate
the second layer increases when the f i r s t layer becomes larger than a certain c r i t i c a l size, but
this size is not unique because i t depends on several factors as vacancy concentration, tempera-
ture, strain f i e l d , etc.

Fig. 3 (b) shows an example of the size distribution for the multilayer G.P.(II) zones
after prolonged aging for 864 ks at 413 K. Since a size distribution can be measured for each Cu
layer (11) the size distribution of the central layer is plotted on the figure. Up to ten layers
could be observed on the micrographs. The result indicates that a l l these multi-layers of G.P.
zones coexist with each other and that their size distributions overlap showing almost a normal
distribution function. This type of size distribution is commonlyobserved for each Cu layer
even when two structures coexist in the early stages of aging.

I f the double-layer structure separated by three Al layers is defined as the G.P.(II) zone,
we can recognize somedifferent features in the structure for the multi-layers, i . e . , the 8"
phase (7,11). However, there is no reason to distinguish a G.P.(II) zone as a d i s t i n c t stage
from that of the B" phase in the aging process. Also, there exists no other reason to d i s t i n -
guish the stage of the G.P.(II) from that of the G.P.(I) zone. From the observations i t is
950 STRUCTURE OF G-P ZONES Vol. 22, No. 7

(a) (b)
N: 264
20

a
1 9: 0.Ixi017

(]6
20 I N: 495
9:0"9xi017
t d

10

Z 10
' ~ ~ dlo

2 6 10 14 18 22 26 2 6 10 14 18 22 26
d (nm) d (nm)

FIG. 3. Distributions in size and structure for G.P. zones in AI-3.9wt%Cu alloy aged for
149.4 ks at 408 K (a) and for 864 ks at 413 K (b). N and n are total and fractional num-
bers of G.P. zones, respectively, d and dm correspond to average diameters of whole of

concluded that the s t r u c t u r a l changes from mono-layer G.P.(I) zones to double-layer G . P . ( I I )

zones and then to m u l t i l a y e r structures (9") is the ideal standard sequence f o r the p r e c i p i t a -
t i o n process (7,11).

However, the images observed occasionally suggest the existence of deviated structures,
although these structures always are not complete (11). I f , f o r example, the double-layer s t r u c -
ture separated only by two AI layers is stacked to form a m u l t i - l a y e r s t r u c t u r e , the r e s u l t i n g
p e r i o d i c i t y produces the same ordered structure as that of the 8' phase and t h i s f a c t may
suggest a p o s s i b i l i t y to form t h i s phase in the growth process.

Structural Modifications Under I r r a d i a t i o n Conditions

Structural modifications occurring during aging under radiation conditions are much larger
compared to those observed during normal aging. An example is given in Fig. 4, where the s t r u c -
t u r a l changes during natural aging under 1.25 MeV electron i r r a d i a t i o n are p l o t t e d as function
of the aging ( i . e . , i r r a d i a t i o n ) time. The sample was pre-aged f o r 360 ks at 413 K where G.P.(I)
zones had already formed. The f o l l o w i n g d i f f u s i o n - c o n t r o l l e d k i n e t i c s are much f a s t e r due to
radiation-induced vacancies. Besides the average zone diameter D the Cu content CCu (at.% Cu)
an~ the ~ensity p of the zones are plotted in the f i g u r e . During the i n i t i a l low dose rate of
101 e/cm~s a s l i g h t increase of D and a larger increase of p and CCu is observed followed by a
decrease of the l a t t e r two parameters. This indicates a beginning d i s s o l u t i o n of G.P. zones.

A f t e r the i r r a d i a t i o n rate of the electron beam has been increased to 1019 e/cm2s, the size
D of the G.P.(I) zones decreases r a p i d l y i n d i c a t i n g a f u r t h e r d i s s o l u t i o n of these zones. At the
same time G . P . ( I I ) zones are developed which grow r a p i d l y to a maximum size followed by a
decrease as seen in Fig. 4. Due to the enhanced d i f f u s i o n s t r u c t u r a l changes toward the more
complex structures occur at a much higher rate. Probably, these structures may contain more
defects compared to those occurring during normal aging. The Cu concentration CCu ( i . e . , the
t o t a l number of Cu atoms present in a l l G.P. zones) is always decreasing showing the r a d i a t i o n -
induced d i s s o l u t i o n which occurs simultaneously during the aging process.
Vol. 22, No. 7 STRUCTURE OF G-P ZONES 951

Fluence ( x1022 e/cm 2 )

0.2
"~--'~ I
0.4
-- I I Ill~, u
I 3
i
5
I | I I
7
I

k
0.12xi019 Ix1019 e/cm 2 S ~-
16
3
P ~\G.P. (II) zone c
0 / o
N
O- 0 G.P.( I) ~zon~D \\ 0

Cl ~Q" -H
12
U
u
a "~'<o 0 2~ I u

0.8

6A
Ch

Cluster
41
D m/m/m o

-~v - - - - v 9
2 >
~J
~V

I I I I I I I I I
20 60 100 140 180
Time ( min )

FIG. 4. Changes of average diameter ~ and density p of G.P. zones in an Al-3.97wt%Cu alloy
during an in-situ HVEMexperiment. CCu (at.Cu) indicates the amount of Cu atoms precipi-
tated to the zones. Cv is the ratio of numbers of vacancies contained in clusters to
those produced in Frenkel pairs.

References

1. A. Guinier, Nature, 142, 569 (1938); Comp. Ren., 206, 1641, 1972 (1938).
2. G.D. Preston, Nature, 142, 570 (1938); Proc. Roy. Soc., A167, 526 (1938).
3. H. Yoshida, H. Hashimoto and Y. Yokota, Electron Microscopy 1978, Vol. 1, p. 306, (1978);
Ann. Repts Res. Reactor Inst. Kyoto Univ., 13, 208 (1980).
4. H. Yoshida, H. Hashimoto and Y. Yokota, Electron Microscopy 1980, Vol. 1, p. 268, Europ.
Cong. Elect. Micros. Fund., The Hague, (1980).
5. H. Yoshida, H. Hashimoto, Y. Yokota and N. Ajika, Trans. Jap. Inst. Metals, 24, 378 (1983).
6. H. Yoshida, H. Hashimoto, Y. Yokota and M. Takeda, Symp. Proc. Vol. 21, p. 131, MRS, (1984).
7. H. Yoshida, Decomposition of Alloys: the early stages, p. 191, Pergamon Press, (1984).
8. T. Sago and T. Takahasi, Trans. Japan Inst. Metals, 24, 386 (1983).
9. N. Ajika, H. Endoh, H. Hashimoto, M. Tomita and H. Yoshida, Phil. Mag. A, 51, 729 (1985).
10. H. Yoshida, D.J.H. Cockayne and M.J. Whelan, Phil. Mag., 34, 89 (1976).
11. H. Yoshida, Phase Transformation, p. 363, (1982).
12. V. Gerold, Z. Metallkde., 45, 593, 599 (1954); Acta Cryst. 11, 230 (1958).