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Acta metall, mater. Vol. 38, No. 2, pp.

351-363, 1990
Printed in Great Britain. All rights reserved

0956-7151/90 $3.00 + 0.00


Copyright 1990 Pergamon Press plc

THE MORPHOLOGY OF PRECIPITATES IN A N A1-Ge


ALLOY--I. EXPERIMENTAL OBSERVATIONS
G. R. H U G O and B. C. M U D D L E
Department of Materials Engineering, Monash University, Clayton, Victoria 3168, Australia
(Received 22 February 1989)

Abstract--The morphology and crystallography of Ge precipitates formed in a quenched and aged


Al 4wt% Ge alloy have been characterized using transmission electron microscopy and electron
microdiffraction. Five different precipitate forms have been distinguished in a sample aged 3 h at 200C:
(i) triangular plates on {11 l}Ai, (ii) laths parallel to (IO0)At, (iii) rods parallel to (l lO)kt, (iv) hexagonal
plates on {lll}A 1, and (v) small regular tetrahedra with {lll}A ~ facets. The cube-cube orientation
relationship, (Tll)c~//(Tll)^I and [tl0]c~//[llO]Al, has been associated with three separate forms of
precipitate: the triangular and hexagonal plates on (T 11)aI and the tetrahedra. A second type of twinned
hexagonal plate has been observed on (T I 1)AI with an orientation relationship deviating from cube-cube
by a rotation of 30 ~ about the habit plane normal, [I1 l]c~. The (IO0)A I laths have [I IO]Ge//[IOO]AI along
their long axis and (T11)~//(O01)Ai; the long axis is an approximately invariant line. Rods parallel to
(llO)A I have in common a rod axis [llO]~//[llO]A~, but several orientation relationships have been
detected, differing by a rotation about this axis. A summary is presented of all precipitate forms and
associated orientation relationships observed in the Al-Ge system.
R ~ u m ~ - L a morphologie et la ,zristallographie de prrcipitrs de Ge formrs dans un alliage A1-4% en poids
Ge tremp6 et vieilli ont 6t6 caractrrisres par microdiffraction 61ectronique. Cinq formes diffrrentes de
prrcipitrs ont 6t6 distingures dans un 6chantillon vieilli 3 h 5. 200C: (i) des plaquettes triangulaires
sur { I 11}AI, (ii) des lattes parallrles 5. (100)A~, (iii) des bfitonnets parallrles 5. (110}AI, (iv) des plaquettes
hexagonales sur {Ill}A~ et (v) de petits trtrardres rrguliers avec des facettes {lll}A ~. La relation
d'orientation mutuelle cube-cube (I11)c~//(I1 l)AI et [110]c~//[110]Ai est associre 5. trois formes distinctes
de prrcipitrs: les plaquettes triangulaires et bexagonales sur (T11)AIet les t&rardres. Un second type de
plaquettes hexagonales maclres 5. 6t6 observ6 sur (T1 l)g~ avec une relation d'orientation drviant de la
prrcrdente par une rotation de 30 autour de la normale au plan d'accolement, [T11]~. Les lattes (100}AI
ont [110]c~//[100]AI le long de leur grand axe et ('i'11)~e//(001)A6 le grand axe est approximativement
invariable. Les b~tonnets parallrles 5. (ll0)AI ont en commun leur axe [ll0]c~//[ll0]A~, mais plusieurs
relations d'orientation, qui diffrrent par une rotation autour de cet axe, ont 6t6 trouvres. Un rrsum6
de routes les formes de prrcipitrs et des relations d'orientation associres pur le systrme AI~Ge est
pr~sentr.
Zusammenfassung--Morphologie und Kristallografle von Ge-Ausscheideungen, die sich in der
abgeschreckten und ausgeheilten Legierung A1-4Gew.-% Ge bilden, werden im Durchstrahlungselektronenmikroskop charakterisiert. Fiinf verschiedene Ausscheidungsformen krnnen in einer fiir 3 h bei
200C ausgelagerten Probe beobachtet werden: (i) dreieckige Platten auf {111 }AI, (ii) Latten parallel zu
(100)AI, (iii) St/ibe parallel zu (110)al, (iv) hexagonale Platten auf {111}aI u n d (v) kleine regelm/il3ige
Tetraeder mit { 111)A,-Facetten. Die kubisch-kubische Orientierungsbeziehung, (1"11)c~//(T1l)al und
[110]c~//[110]At kann drei getrennten Ausscheidungsformen zugeschrieben werden: den dreieckigen und
den hexagonalen Platten auf (lll)Ai und den Tetraedern. Ein zweiter Typ, verzwillingte hexagonale
Platten, wird auf (1"11)At mit einer Orientierungsbeziehung beobachtet, die vonder kubisch-kubischen
durch eine Rotation um die Normale der Habitebene [[ll]c~ um 30. Ffir die (100)AI-Latten gilt
[110]c~//[100]Al entlang der langen Achse und ('i'11)~//(001)A t . Die lange Achse ist nfiherungsweise eine
invariante Linie. Die St/ibe parallel zu ( l l 0 ) a I haben eine gemeinsame Stabachse [I 10]c~//[110]a6
allerdings wurden mehrere Orientierungsbeziehungen aufgefunden, die sich in einer Rotation um diese
Achse unterscheiden. Die im AI-Ge-System beobachteten Ausscheidungsformen und die damit zusammenh/ingenden Orientierungsbeziehungen werden zusammengefal3t dargestellt.

l. INTRODUCTION

in an anisotropic crystalline matrix. In recent research


[1, 2], the important role of crystal symmetry has been
emphasized and it has been proposed [1] that, for
many precipitation reactions, it is possible to interpret the precipitate shape in terms of the point
symmetry of the matrix and precipitate phases and
the orientation relationship that exists between them.
Briefly, this analysis considers two crystals in a given

The morphology of a precipitate phase and the


orientation of the precipitate lattice with respect to
the surrounding matrix lattice are factors which have
a significant bearing on microstructure-property relationships. There are, in turn, many factors which
determine the shape of a precipitate crystal growing
351

352

HUGO and MUDDLE: PRECIPITATES IN AN A1-Ge ALLOY--I

orientation relationship, separated by a planar interface with normal n. A symmetry operation performed
on this system with an operator that is common to
both crystals in this orientation will restore precipitate and matrix crystals independently to congruence,
but transform the normal n to an orientation n',
crystallographically equivalent to the original. If this
procedure is repeated for all such common symmetry
elements, then all possible orientations of the interface will be defined, generating a form for the precipitate crystal that is compatible with symmetry.
Those point symmetry elements common to precipitate and matrix crystals in the observed orientation relationship constitute the intersection point
group, H. The point group H defines [1] effectively the
symmetry of the Wulff plot, which is commonly
employed to define the equilibrium shape of a precipitate nucleus [3, 4]. The proposal which thus emerges
is that the morphology of a solid state precipitate
must be consistent with the symmetry of the intersection group, H. The intersection point group
may be determined simply by inspection of superimposed stereographic projections of the precipitate
and matrix crystals in the observed orientation relationship. This symmetry analysis has been applied
to precipitates in a limited range of metallic and
ceramic alloys [1, 5-10] and shown to account successfully for the observed morphologies. The purpose
of the present work was to determine the applicability
of the analysis to the range of precipitate forms
observed in the AI-Ge system.
The A I - G e system has a number of features which
make it interesting for study in this context. The
equilibrium phase diagram is a simple eutectic with
the terminal phases comprising an Al-based solid
solution and nominally pure Ge. The solid solubility
of Ge in A1 is a maximum 6.9 wt% [11] at the eutectic
temperature (424C) and decreases rapidly with decreasing temperature to < 0 . 5 w t % at 200C. For
dilute alloys of Ge in AI, solution treated, quenched
and aged in the temperature range 50-250C, precipitates of essentially pure Ge form directly from
supersaturated solid solution, apparently without formation of any intermediate metastable phases. These
precipitates adopt a variety of morphologies depending largely on the conditions of heat treatment
[6-8,11-13]. In a study of a 4 . 5 w t % G e alloy,
Lorimer and Nicholson [11, 13] have reported that
samples aged at 140C contained predominantly triangular platelets of Ge on {111}A~planes with edges
parallel to (110)AI, and truncated {1 l l}A1 platelets
with edges parallel to both (110)Al and (100)Ai.t In
each case the Ge lattice was reported to have an
identity (or cube-cube) orientation relationship with
that of the matrix phase. For ageing at higher temperatures ( > 200C), rod-like precipitates parallel to
(100)al were more commonly observed. K6ster [14]
fThis result is recorded as reported [11], but it is noted that
(100)A t directions do not lie in {111}Aj habit planes.

observed similar morphologies in an AI-3.4 wt% Ge


alloy, along with large rectangular plates on {100}A1
planes. The triangular plates were again favoured at
lower ageing temperatures ( < 150C), whilst the rods
were predominant at 250C. The identity orientation
relationship was also reported for the triangular
plates, whilst that for the (100)A~ rods was given as:
(111)Ge//(001)A1 and [0T1]Ge//[010]Aj. The large plates
were produced by ageing just below the solvus
temperature or by direct quenching to an ageing
temperature of 250C and exhibited an orientation
relationship
in
which
(T11)Ge//(001)A1 and
[110Ice//[110]A I .
Recently, Dahmen and Westmacott [6-8] have
examined Ge precipitates in an AI-2.6 wt% Ge alloy
using high resolution electron microscopy and observed mainly rod-like precipitates parallel to (100)k l
directions. The rod axis was invariably a (ll0)Ge
direction, and a series of orientation relationships
were distinguished, differing by a rotation about the
rod axis. The most common was similar to that
reported by K6ster [14] for (100)A I rods. When
observed parallel to the rod axis, the ( 1 0 0 ) A l rods
were found to exhibit multiple internal twins, with
twinning planes invariably containing the rod axis.
For certain (100)gl rods of Ge, this multiple twinning
extended to 5-fold twins about the rod axis [7, 8, 15].
In the present study, the crystallography and morphology of Ge precipitates formed in a quenched and
aged A l - 4 w t % Ge alloy have been characterized
using transmission electron microscopy and electron
microdiffraction. The results are presented in two
parts; Part I includes the experimental observations
for each of five distinct precipitate morphologies
identified, while Part II details the symmetry analysis
for each of these precipitate shapes.
2. E X P E R I M E N T A L P R O C E D U R E S

An alloy of nominal composition A1-4.0 wt% Ge


was prepared from 99.99% purity aluminium and
99.999% purity germanium by induction melting
under a partial atmosphere of argon and chill casting
into a cast iron mould. The alloy was homogenized
for 22h at 437C, and then cold rolled to strip
approx. 0.4mm thick. Specimens were solution
treated at 430C for 4h, water quenched to room
temperature and then aged at temperatures between
150 and 200C in an oil bath. Thin foil specimens for
transmission electron microscopy were prepared from
the aged material by the twin-jet electropolishing
technique, using a solution of 40 v/o acetic acid,
30 v/o orthophosphoric acid, 20 v/o nitric acid and
10 v/o water, operating at 12 V (0.2 A) and 20C. The
microstructures were examined in a Philips EM420
transmission electron microscope operating at
120 keV. Electron microdiffraction was used to obtain diffraction information from individual precipitates, the microscope being operated in conventional
transmission mode with a 30 or 5 0 # m condenser

HUGO and MUDDLE:

PRECIPITATES IN AN AI-Ge ALLOY--I

353

aperture and an electron probe nominally 40-100 nm


in diameter.
3. EXPERIMENTAL RESULTS

Following preliminary observations, a specimen


aged 3 h at 200C was selected for detailed microstructural characterization. This treatment produced
a range of precipitate shapes of a size amenable to
study using the electron microdiffraction technique
(i.e. typically 100 nm). The form and distribution of
precipitates were observed to vary both from grain to
grain and locally within grains, there commonly
being some grains or regions of grains in which plate
shapes on {lll}A l planes were predominant, and
others in which rods or laths parallel t o (I00)A l or
(110)A~ directions appeared favoured. A precipitatefree zone was common along grain boundaries, with
relatively coarse Ge precipitates intruding into the
boundar3 of this zone. The scale of precipitates
generally decreased and the density of precipitation
increased with distance from the grain boundary,
although there remained local variations within
grains. A correlation was observed between the morphology and density of precipitates, with the less
densely populated regions containing predominantly
(100)A ~ Laths and i110)a~ rods and those regions of
high density being populated by finer scale precipitates with planar (111)AI facets. It proved possible to
distinguish five different morphologies of Ge precipitate in this one specimen: (i) triangular plates on
{ 1 l l}A1planes, (ii) laths parallel to (100)A1, (iii) rods
parallel to (110)A L, (iv) hexagonal plates parallel to
{11 l}Al, and (v) small regular tetrahedra with {111}A1
facets.
The crystallography for each of these prominent
precipitate types was characterized in detail as a basis
for subsequent symmetry analysis.

3. I. Triangular plate morphology


Precipitates of triangular plate morphology are
shown in Fig. 1. projected normal to (a) (111)A l and
(b) ( l l 0 ) A L zone axes. These precipitates exhibit a
range of sizes, with the larger plates having a side of
typicall) 70-100 nm. In addition to those plates of
triangular section inclined at an angle of approx. 35
to the ( l l 0 ) A 1 zone axis, Fig. l(b) includes two sets
of plates parallel to the zone axis (i.e. 'edge-on') and
separated by an angle of ~ 70 ~. It is thus clear that
the plates have a 'Llll }AI habit plane and, as shown
in Fig. l(a), are bound by ( l l 0 ) A l directions, Some
of the triangular plates, particularly the larger ones,
have each apex truncated parallel to the (ll0)Al
direction bounding the opposite face. For a given
{ 111 }ALhabit plane, there appear two variants of the
triangular form (A and B, Fig. 1) distinguished in
tFor superimposed ,( 111 ) zone axis patterns the orientation
relationship may be cube-cube [12-14], or differ from it
by a rotation of 60: about the common ( 111 ) directions.

Fig. 1. Transmission electron mirographs showing Ge precipitates of predominantly triangular plate morphology
projected normal to (a) (111 )Al, and (b) (110)Ai zone axes.

appearance by an operation of inversion (or a rotation of 180 about the habit plane normal). Electron
microdiffraction patterns recorded from individual
triangular plates parallel to (111)A1 and (001 )AI zone
axes are reproduced in Fig. 2, indexed in accordance
with the f.c.c. (a = 0.4050 nm) and diamond cubic
(a = 0.5658 nm) lattices of pure AI and Ge respectively. The superimposed (111) patterns, Fig. 2(a),
do not permit an unambiguous solution for the
orientation relationship.? However, the patterns in
Fig. 2(b) indicate that [00116e and [001]A~ zone axes
are also parallel, confirming that the orientation
relationship is cube-cube.

3.2. (100) Lath morphology


A second common morphology for Ge precipitates
was that of laths extending parallel to (100)A1 directions. Examples are shown in Fig. 3, in projection
normal to an (001)A~ zone axis. These precipitates
were typically 1 p m in length and their projected
widths varied from 20 to 150nm. They could
be classified into two groups, either "broad" or
"narrow", according to their projected widths. This
distinction was confirmed crystallographically in electron microdiffraction patterns recorded from parallel
laths in the two categories, parallel to an (001)A~ zone
axis, Fig. 4. The patterns from the precipitate phase
are distinguishably different; that in Fig. 4(a) represents a (111)Ge zone axis pattern, whilst in Fig. 4(b)

354

HUGO and MUDDLE: PRECIPITATES IN AN A1-Ge ALLOY--I


+

+I

++

+1

m +

+0

+
+l

m+o +

0+

0+

+ + +

++ 0+ +

+0

o+

+m

+
+

0+

+
+

AI [-{11] zone

Double diffracted reflections

Ge ~ 1 1 ] zone

~)i!i

+
+

Q%

*
Q

+
t

+
+

++

++
+

+
+

020Ai

m~

+~'~-040Go

+
- - ~ " - -+- ' - - r+~ 220Ge

200AI
~
+
+

+ + ~/+
#
++

+000+

+ + +

+
+

+ +

o*

~_

+ +
+

:e

4OO

+
+

AI [001] zone

Ge [001] zone

Double diffracted reflections

Fig. 2. Electron microdiffraction patterns for Ge precipitates of triangular plate morphology showing:
(a) [I1 l]c~//[I11]A1 and (b) [001]c,,//[001]AI.

the electron beam is parallel to (112)4. However,


both pairs of superimposed precipitate and matrix
patterns are consistent with a single orientation relationship in which
(TI l)c~//(001)a t and
[ 110]Ge//[ 100]at.

Fig. 3. Transmission electron micrograph showing Ge laths

parallel to (100)AI; B ~ (001)A I.

The long axes of both precipitates are parallel to


[100]~a (//[ll0]c~) and they represent two equivalent
variants of the orientation relationship differing by a
rotation of 90 about this axis. The habit plane of the
laths is (001)~a and the distinction that is drawn
between the broad and narrow precipitates corresponds to observation of a lath morphology either
normal or parallel to the habit plane respectively. The

HUGO and MUDDLE:

PRECIPITATES IN AN A1-Ge ALLOY--I

++

++

II
+

355

m000

1
+

020A ~

++

~_

200AI

- +
022GO

220Ge

++

O+

~-

250 nm

AI [0011 zone

Ge ~11] zone

Double diffracted reflections

I1

.,~---~11Ge
+ 1

OR

+O- ~
000

002A I

DO

200AI
220Ge

AI [010] zone

Ge [172] zone

Double diffracted reflections

Fig. 4. (a) Broad (I00)AI Ge lath and corresponding microdiffraction patterns in which [TI 1]~//[001]A6
(b) narrow (100)A ~ Ge lath (centrefield) and corresponding rnicrodiffraction patterns in which
[1r2]c~//[0]'0]A~.

precipitate morphology consistent with experimental


observations is represented schematically in Fig. 5.
As indicated, initial observations would suggest that
there should be two crystallographic variants of the
precipitate phase on a given {001 }A1 habit plane and
thus a total of six variants in a given orientation of
the matrix phase.
The preferred growth of these laths along [100]a I is
attributable to the low misfit ( ~ 1.2%) in interatomic
spacing in parallel directions [110]Ge and [100]a ~. This
is to be compared with a misfit of approx. 14% along
directions normal to this in the habit plane (i.e.
[]'l~]Ge//[020]Al) and of approx. 21% parallel to the
habit plane normal. It is also noted that the laths were

commonly truncated at either end approximately


parallel to (101)~,.

3.3. (110) Rod morphology


Precipitates were also observed in the form of long,
thin rods parallel to matrix (110) directions, Fig. 6.
These rods were typically l-2/~m in length, with a
projected width of approx. 35 nm. The latter dimension appeared to be largely independent of the plane
of projection, confirming the rod-like morphology.
The (110)Al rods invariably had a ( 1 1 0 ) ~ direction parallel to the rod axis, but a range of orientation
relationships was observed, the various relationships
differing by a relative rotation about the rod axis. The

356

HUGO and MUDDLE: PRECIPITATES IN AN A1-Ge ALLOY--I

a.

1111]Ge

b.

[oo~l~

[100]~ ~

[010]~

Fig. 5. Schematic representation of (a) (100)A I lath morphology for Ge precipitates and associated orientation
relationship, and (b) six variants of lath morphology distinguishable macroscopically in a given matrix orientation.
microdiffraction patterns recorded from the rod in
Fig. 7 may, for example, be indexed in accordance
with an orientation relationship in which
(I10)Gd/(001)~a and
[110]c~//[110]m//rod axis.
This relationship is shown in stereographic projection
in Fig. 8. In contrast, the patterns recorded from the
rod in Fig. 9 indicate an orientation relationship in
which
(~21)Ge//(001)A l and
[110]c~//[110]Al//rod axis.
These two relationships differ by a rotation of 19.5
about the common ( l l 0 ) directions parallel to the
rod axis, Fig. 8. Examples were also detected of a
third relationship in which [l 10]Ge//[110]AIand (I 11)c~
is approximately parallel to (001)~. It would seem
that the ( l l 0 ) A | rods may adopt a range of orientation relationships characterized by a common rod
axis (i.e. [ll0]Gd/[ll0]~), but in which the relative
rotation of precipitate and matrix lattices about this
axis is not determined uniquely.

3.4. Hexagonal plate morphology


In addition to equilateral triangular plates, a series
of precipitate forms ranging from truncated triangles
to regular hexagons were observed on { 111 }~a planes.
The variation in morphology appeared to be near
continuous and the cube-cube orientation relationship characteristic of the triangular plate morphology

Fig. 6. Transmission electron micrographs showing thin Ge


rods parallel to (I10)Aj directions in (001)Al projection.
was found to be preserved in some {Ill}Al plates
with nearly regular hexagonal shape. An example of
such a plate and the corresponding microdiffraction
pattern is shown in Fig. 10.
A separate hexagonal plate morphology parallel
to {11 I}Aj planes was also distinguished on the basis
of orientation relationship. Figure 11 shows a typical
example of such plate and electron microdiffraction
patterns recorded from these plates parallel to
( l l l ) A I and (l12)A l directions are reproduced in
Fig. 12. The orientation relationship between precipitate and matrix lattices is, in this case, such that

(il 1)ce//(il

l)Ai//habit plane, and

[21 l]Ge//[110]A I.

This differs from the cube-cube relationship by a


rotation of 30 about the common [ i l 1] axis normal
to the habit plane of the plate. Despite this distinction
in lattice orientation relationship, the facets of the
hexagonal plates remain bound by edges parallel to
(110)~ directions, as is the case with the truncated
triangles.
It is noted that the microdiffraction pattern in
Fig. 12(a) contains reflections which are not normal
components of a [Ill]~o zone axis pattern from a
Ge single crystal. These additional reflections imply
an interplanar spacing of 0.34 nm, greater than the
maximum interplanar spacing for the Ge lattice
(d = 0.327nm), and equivalent to three times the

HUGO and MUDDLE:

PRECIPITATES IN AN A1-Ge ALLOY--I

71o-

357

_ _

221a,
gg...._._.~ 2 ~ a 0

1TOAI

Axis

221Ge

110AI

001AI

110AI

221Ge

Fig. 8. Steregraphic projection showing orientation relationship for (110)k I Ge rods in which (]'10)c.e//(001)g I and
[ll0]6e//[ll0]A1. The relative rotation about the rod axis
[ l l 0 ] g I required to produce the alternative relationship,
(~21)Ge//(001)AI and [11016e//[110]AI, is indicated.

v -I..
+

+-_-_

b
"~+ +
I~
+

~+

+
+ -~

-~

+ 0+ +

[]

+ ++

+
+ +O +

++

+
[] +
+
+

+
+
+
+

+
+
+
+
0

+
~

+0+
+

++ * + + +,
+
+
o+o0+ + + * %
+

++-+~

+ ~
~

+/--,/,o

+_
+

++
O+

+l, +-

+ +. / + ++/+/~+/o+ \+o+ +o
+

[]

/+

//+

/+

+~

+L:_//. "+L-I + , 002Ge/_I~2OOAI

220Get-220AI

AI [001] zone

Ge [110] zone

Double diffracted reflections

Fig. 7. (a) Transmission electron micrograph of ( l l O ) A I


Ge rod, and (b) corresponding electron microdiffraction
patterns showing [TlO]c~//[OO1]Ai.
AMM 38,2--N*

Fig. 9. (a) Transmission electron micrograph of ( l l 0 ) A l


Ge rod for which superimposed electron microdiffraction
patterns (b) indicate [~21]Ge//[001]A].

358

luu nm

HUGO and MUDDLE: PRECIPITATES IN AN AI-Ge ALLOY--I

B--- 001

relrod of this magnitude would imply diffraction


from a crystal limited in thickness to the order of
10A, which corresponds to three (]'ll)Ge planes.
Given the observed intensities of the Ge reflections
relative to the matrix reflections (Fig. 12) and the
strong bright field contrast observed for the plates
(Fig. 11), the possibility of 10A thick plates is
discounted. It is proposed that the streaking of the
{ 111 }Ge reflections is due to disruption of the stacking
sequence of (T11)ce planes by very fine scale twinning
and/or faulting of the Ge plates on the (I11) planes
parallel to the habit plane. The spacing of the twins
or stacking faults implied would be of the order of
10/~, or 3-5 (Tll)c e planes.
An alternative approach to accounting for the
additional reflections emerges when the consequences
of twinning or faulting on the proposed scale are
examined more closely. The disruption to the ABCA
stacking sequence of (111)~ e planes associated with
twinning (or faulting) on every 3-5 planes is sufficient
to permit alternative descriptions of the structure of
the Ge. It is easily shown, for example, that for
regular periodic twinning on every five (i 11)ce planes,
the resulting twinned diamond cubic structure may be
equally well described as an hexagonal crystal. The
basal plane of the hexagonal structure would be
parallel to the (11 l)c e twinning plane and the hexagonal unit cell would consist of an ABCABCBACBA
stacking sequence of close-packed planest with a
lattice parameter c equivalent to 10 times the interplanar spacing of cubic (iI1)G e planes (i.e.
c = 3.27 nm). Electron diffraction patterns have been
computed for a series of hexagonal structures derived
from the Ge diamond cubic structure by regular
twinning on (ill)G planes. As shown in Fig. 12,
calculated patterns for those structures featuring
twinning on every four or five (i 11)c ~ planes simulate
closely the observed electron microdiffraction patterns. Similar calculated diffraction patterns were
obtained for hexagonal structures derived by inserting (Tl 1)Ge stacking faults into the Ge structure on a
similar scale. It should be noted that the calculated
patterns are for structures derived by twinning or

Fig. 10. (a) Transmission electron micrographs depicting


two variants of hexagonal precipitate plates parallel to
{lll}a 1, and (b) associated electron microdiffraction patterns. The patterns show [001]c~//[001]aI and are identical
with those of Fig. 2(b)
spacing of {224}c o planes. They cannot be accounted
for as products of multiple diffraction, but it is
possible to associate them with streaking of { 11 l}c ~
reflections in a direction normal to the plane of the
plates (i.e. { 111 }~o reflections above or below the zero
layer for the [il 1]c~ zone). The distance in reciprocal
space from the nearest { 111 } reciprocal lattice point
to the zero layer in the [ill]Ge zone is 0.10,~ -l. A
50 nm

tNote that two Ge atoms are associated with each lattice


point in these close-packed planes,

Fig. 11. Transmission electron micrograph showing small


hexagonal precipitate plate (arrowed) on {I1 l}aI.

HUGO and MUDDLE:

PRECIPITATES IN AN AI-Ge ALLOY--I

0 ~ AI

Ge
220
.

000

202Ge

I
022Ge

000

220 AI

422Ge

220A1

422Ge

111 Ge

359

n 311AI

T~TAI

d
202 AI

Fig. 12. (a), (b) Electron microdiffraction patterns from hexagonal precipitate plate of the type shown in
Fig. I1, (c) schematic solution to (a) with [Tll]~//[Tll]AI, and (d) schematic solution to (b) with
[~13]c~//[T12]aj. The schematic patterns have been computed for a hexagonal structure derived from the
Ge diamond cubic lattice by regular twinning on every five (T11)c~planes. Note that only those reflections
occurring in normal [T11]c~and [~13]~ zone axis patterns are indexed; the additional reflections arise from
fine-scale twinning or faulting parallel to (I1 l)c~.
faulting at regular, periodic intervals. It was not
possible to readily simulate diffraction patterns for
structures arising from random twinning or faulting.
However, it is to be anticipated that similar results
would be achieved lbr structures randomly twinned
or faulted, provided that the average separation of
the planar defects was on the same scale.
For an hexagonal plate observed parallel to the
[l12]A ~ zone axis and with the above orientation
relationship between precipitate and matrix phases,
the electron beam will be close to a [~13]Ge zone axis
in the precipitate phase. The expected electron
diffraction pattern for the two variants of the precipitate phase which are twin-related across (Tll)o e is
shown in Fig. 13. Comparison with the observed
diffraction pattern, Fig. 12(b) indicates that significant amounts of both variants are present in the
precipitate. This suggests that the structure is
twinned, for if the disruption to the (11 I)Ge stacking

was due to stacking faults alone, the expected diffraction pattern would show strong reflections for a single
variant only, with much weaker intensity for those
reflections corresponding to the alternative variant,

3.5. Precipitate tetrahedra


The existence of small Ge precipitates having the
form of regular tetrahedra was confirmed by tilting
the sample systematically and observing changes in
the projected shapes of the precipitates. Figure 14
shows one such sequence of micrographs for which
the tilt axis is approximately horizontal. With the
electron beam close to a <112)Al zone the precipitate
projects as a triangle, Fig. 14(a), whereas on an
<001)A 1 zone the projected shape is a square,
Fig. 14(d). For small tilt angles ( ~ 10) either side of
the <001 >A~zone, Figs 14(c, f), the projection of the
tetrahedral form is revealed clearly. From these
and other micrographs it was established that the

360

HUGO and MUDDLE: PRECIPITATES IN AN A1-Ge ALLOY--I

[16, 17] following quenching and in the early stages of


ageing and models for precipitate nuclei developed
+
*
[8, 18] on the basis of co-precipitation of Ge atoms

-1+
I
and vacancies in appropriate ratios. It has been
@ +0
+

0
suggested [8] that the variation in precipitate mor+ @+
0
+ + + +
+ + + 4-t+
phology may be associated with differences in the
required vacancy concentration for a given form and

1000
I~@422 Ge
local variations in vacancy supersaturation in the
+ + 4- +
+
+
+ + +~+
matrix phase. It appears likely that the restricted size
0 4- +
0
e1"11Ge 0 + ~ O
of each of the observed shapes is to be attributed to
+
I I~'IAI
+~1220AI
the large volume accommodation that must accom4-Ipany growth.
+
+ + 4-I+
4- + + +
A summary is presented in Table 1 of those
orientation relationships that have been observed for
Ge precipitates in A1-Ge solid solution and the

AI ~12] zone
precipitate morphologies associated with them. The

Gevariant 1 ~13] zone


cube-cube relationship (1) is exhibited by those
0 Gevariant 2
shapes with dominant planar interfaces parallel to
common
close-packed {11 I}Al planes in precipitate
+ Double diffracted reflections
and matrix phases. The most common is that of
Fig. 13. Schematic electron diffraction pattern expected for
[I 12]A~AI zone axis 19.5 from the habit plane normal [TI 1]A1 triangular plates on {111}AI planes, as observed in
of hexagonal plates. Superimposed Ge zone axis patterns previous studies [13, 14]. The present observations
correspond to variants twin-related about ('fll)c~.
indicate that there are two variants of these plates on
a given {11 I}A~habit plane and thus a potential eight
tetrahedra are bound by {111}AI facets, with edges variants in a given orientation of the matrix phase.
parallel to close-packed (ll0)Al directions, Figs Many of the larger triangular plates have each apex
14(d, e). Although not shown here, the shape of a truncated parallel to the opposite edge (i.e. parallel to
tetrahedron projected parallel to a (111)Aj zone axis (ll0)Al) and there appears an almost continuous
would be that of an equilateral triangle and thus variation in morphology from equilateral triangles to
difficult to distinguish from the triangular plate mor- near regular hexagonal plates in which the cube-cube
phology in this orientation. Similarly, the square relationship is maintained. An interesting new obsershape observed in (001)A~ orientation might be mis- vation is that of fine-scale precipitates in the form of
interpreted as the projection of a cuboid or a (100)Al regular tetrahedra with { 111 }Al facets, for which the
rod of square section observed parallel to the rod lattice orientation relationship is also cube-cube.
It is well recognized [8, 18] that the lattice parameaxis. The tetrahedra typically had edges 30-50 nm in
length, extending occasionally to 100 nm.
ter ratio ace:aAl is almost exactly 7:5. For those
The electron microdiffraction pattern recorded precipitates with cube-cube orientation relationship
from the precipitate tetrahedron (Fig. 14) parallel to and planar interfaces parallel to common closean (001)AI z o n e axis is reproduced in Fig. 14(e). This packed {111 } planes, this ratio thus applies to interis equivalent to patterns obtained from precipitates of atomic spacings along parallel directions within these
triangular plate morphology (Fig. 2) and may be planes in Ge and matrix lattices. Provided that an
indexed unambiguously in accordance with a cube- adequate supply of vacancies is incorporated into the
cube orientation relationship between precipitate and precipitate phase to accommodate the volume expansion accompanying growth, this lattice corresponmatrix phases.
dence may be sustained parallel to the interphase
boundary to create an extended interface that is
4. DISCUSSION
almost strain free. The residual misfit, based on lattice
The precipitation of Ge from supersaturated parameters of the pure constituents measured at
AI-Ge solid solution requires a change in crystal ambient temperatures, is approx. 0.2%.
Departures from the cube-cube orientation restructure (face-centred to diamond cubic) and large
increases in lattice dimensions and average atomic lationship occur either by a rotation about the
volume (A~ = 36%). However, irrespective of shape, normal to common close-packed planes (T11) or by
Ge precipitates exhibit little or no evidence of exten- rotations about a single pair of common close-packed
sive plastic or elastic accommodation of this volume [110] directions in these planes. A relative rotation of
change. It has thus been inferred [8, 11, 16] that 30 about [ill]ce (//[Tll]AI) generates the new revacancies are essential to nucleation and growth, the lationship (2) observed for hexagonal plates of (T 11)~
volume expansion being accommodated by the incor- habit plane. In this case (112)G e directions are now
poration of vacancies in adequate concentrations in parallel to those (110)Aj directions defining the edges
the precipitate phase. Evidence of an interaction of the plates in the habit plane. The relationship
between Ge atoms and vacancies has been detected preserves parallelism of the close-packed planes, but

HUGO and MUDDLE:

PRECIPITATES IN AN AI Ge ALLOY--I

361

Fig. 14. Sequence of micrographs showing small tetrahedral precipitate tilted systematically about [110]AI .
(a) [l12]A], (b) ~7 from [TI2]A 1 towards [00I]AI, (C) ~23 from []'12]Al towards [001]At, (d) [00I]AI,
(e) corresponding [001]A 1 z o n e axis pattern, (f) ~ 16 from [001]AI towards [l]'2]g].
apparently increases the misfit in interatomic spacing
along parallel directions within these planes. Careful
analysis of microdiffraction patterns from individual
Ge precipitates in this orientation indicates that the
plates are twinned parallel to the habit plane on the
scale of approximately every 4-5 (lll)Ge planes.
There are thus a potential eight crystallographically
equivalent variants of the precipitate phase in a given
orientation of the matrix phase.
Those orientation relationships (3-5, Table 1)
differing from cube-cube by relative rotations of

precipitate and matrix lattices about [ 110]A~(//[1 10]G~)


preserve the 7:5 correspondence in interatomic
spacings along these directions and are identified with
precipitate forms elongated parallel to [110]A1. In the
present work, these relationships have been associated with a new morphology in the form of long thin
rods parallel to (110)A 1. However, for that relationship designated 3, the more common precipitate form
appears to be that of large, rectangular plates on
(0 0 1 )A I, with long edges parallel to [110]A1 and ( i l 1)~e
facets parallel to the habit plane [14]. Such plates

362

HUGO and MUDDLE: PRECIPITATES IN AN AI-Ge ALLOY--I

Table 1. Summaryof orientationrelationshipsreportedfor Ge precipitatesin AI~Gealloysand the


associatedprecipitatemorphologies
(1"11)Ge// 011)AI
[110] Ge // [110]AI
TrlangularPlateson 1111}A,
HexagonalPlateson {111}Al

1I
30 Rolation

I
~;
I[111] Gel/ ~11]A I I HexagnalPlatesnO11)Al

Tetra . ra ou . .(1111.,

--

,50Rotation

[110] CO// [110]

R::a7n

[ (~11)Ge fl ~11)A!
I [211] Ge// [110]AI

[OOl1Ge// [OOll~j
(~11)Ge // (001)AI
[1101Ge// [110]AI

45o Rotation

I (~11)Ge# (O01)AI
11101Ge// IIOOIAI

LargeRectangularPlateson (001)AI [ [1-111Ge// [001]AI t,.[ [IOOIAI Laths

/
15"8 /

[1101Ge// [1101Aj

Rotation

(221)Ge// (O01)AI
[11o1Ge// [1101Ai

I 9.7o

Rotation

('110)Ge// (011)AI
[110} Ge// [100]AI
[lOO]At Rods

[110]AI Rods

01

19.5
Rotation

[1101Ge/,I [IO0]AI

[1101Ge # 11101Ai

(1o) Gea (001)Aj


[110] Ge// [110]A I

l 450
1110]Ge fl [100]AI Rolation
I

11101AI Rods

were not observed in the present work, but this is


undoubtedly attributable to evidence that they are
only produced at higher ageing temperatures
(>250C) and most commonly as a result of direct
quenching from the solution treatment temperature
to the ageing temperature [14]. That relationship
(4) for which (~21)Ge//(001)AI and (lil)~o//(lii)Al is
recognizable as equivalent to the twin orientation
relationship common to cubic crystals [19] and has
been observed previously [20] for precipitates of
r/-carbide (il2C) with diamond cubic structure in a
complex N i - F e - W alloy.
In an earlier study, Krster [14] reported the
existence of rod-shaped Ge precipitates parallel to
(100)AI, with an orientation relationship (6) in which
(i11)Ge//(001)A1 and [110]Gd/[100]Al. The present evidence suggests, however, that such precipitates are
more correctly described as laths with an (00 l)At habit

(OOl) Ge// (001)Ai


11101Get/ [100]AI

8/

Plateson (O01)AI

plane and a long axis parallel to [100]A1 (i.e. [110]c~).


Observations based on morphology alone, Fig. 5,
suggest that there are a potential six variants in a
given matrix orientation. The preferred growth of
laths along (100)~ is readily attributed to the compatibility of precipitate and matrix lattices along
parallel directions [ll0]Ge and [100]^ 1. For lattice
parameters measured at room temperature, the misfit
in interatomic spacing is approx. 1.2%.
In addition to observing similar precipitates,
Dahmen and Westmacott [6-8] have reported at least
one example [8, 21] of a lath-shaped particle in which
the orientation relationship is identical, but for which
the extended facets defining the habit plane are
{lll}G e planes parallel to {310}At. They have also
identified a further two major orientation relationships (7,8) which preserve the relationship
[110]Ge//[100]Al, but differ from the above orientation

HUGO and MUDDLE:

PRECIPITATES IN AN AI-Ge ALLOY--I

relationship (6) by rotations about this axis. A relative rotation of the Ge lattice by 9.7 renders
(T10)Ge//(011)AI, and a further rotation of 45
has (001)Ge//(001)A 1. The corresponding precipitate
morphologies appear to be rods parallel to [100]AI and
platelets on (001)A 1 respectively, although the latter
has only been justified on the basis of symmetry
analysis [6] and has yet to be confirmed experimentally. Observed parallel to the long axis, the (100)A ~
rods or laths invariably contain internal twins on
{ l l l } G e planes parallel to the long axis [6-8]. For
s o m e ( 1 0 0 ) A 1 rods, complex multiple twins with
approximate 5-fold symmetry have been detected
[7, 8] along the rod axis; such twinning was not
observed in the present work.
It is finally interesting to note that those orientation relationships designated 5 and 7 in the present
survey (Table 1) are equivalent crystallographically,
but associated with rod-shaped precipitates parallel
to different directions in the matrix phase. Further
discussion of the variation in orientation relationship
and precipitate morphology will follow the symmetry
analysis reported in Part II [22].

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