Acta mater. Vol. 47, No. 17, pp.

43874403, 1999
# 1999 Acta Metallurgica Inc.
Published by Elsevier Science Ltd. All rights reserved.
Printed in Great Britain
PII: S1359-6454(99)00250-5 1359-6454/99 $20.00 + 0.00

THE EFFECT OF VANADIUM AND GRAIN REFINER

ADDITIONS ON THE NUCLEATION OF SECONDARY
PHASES IN 1XXX Al ALLOYS
C. M. ALLEN 1{, K. A. Q. O'REILLY 1, P. V. EVANS 2 and B. CANTOR 1
Oxford Centre for Advanced Materials and Composites, Department of Materials, University of
1

Oxford, Parks Road, Oxford OX1 3PH, U.K. and 2Alcan International Limited, Banbury Laboratory,
Southam Road, Banbury, Oxfordshire OX16 7SP, U.K.

(Received 11 March 1999; accepted 31 July 1999)

AbstractHigh purity Al0.3 wt% Fe0.1 wt% Si alloys with dierent Si, V and grain rener contents
were melt spun to produce microstructures of submicron secondary phases entrained in a higher melting
point Al matrix. On reheating, a dispersion of eutectic liquid droplets forms that represents an exaggerated
version of the liquid puddles that solidify pinched-o between Al dendrite arms during conventional cast-
ing. The subsequent resolidication of the droplets, analysed using dierential scanning calorimetry (DSC),
allows the nucleation-controlled aspects of secondary phase selection to be studied. The droplets solidify as
the metastable FeAlm phase in ribbons containing 2500 ppm V or 2100 ppm V plus AlTiB, AlTiC
or AlB grain rener. This phase contributes to the ``r-tree'' surface defect in commercial sheet products.
This work suggests that the combination of V and AlTiB promotes FeAlm in commercial ingots, and
conrms that solidication rate and bulk Si content also inuence phase content. # 1999 Acta Metallur-
gica Inc. Published by Elsevier Science Ltd. All rights reserved.

Keywords: Aluminium alloys; Casting; Dierential scanning calorimetry (DSC); Nucleation; Rapid
solidication

1. INTRODUCTION directional solidication techniques such as

Wrought Al alloys are used in a variety of commer- Bridgman growth [510] or surface melting and
cially important applications, including packaging, regrowth, using either laser melting [11] or electron
beverage cans, extrusions and automotive com- beam melting [12]. In general, however, the mechan-
ponents. The secondary phases in these alloys, isms by which these phases nucleate prior to growth
although often present at <5 vol.%, can aect ma- have not been investigated systematically. Cantor
terial properties including strength, toughness, ano- and co-workers [13] have developed a modied
entrained droplet method [14] combined with dier-
dising response, formability and recrystallisation.
ential scanning calorimetry (DSC) to study the het-
Most wrought Al alloys are direct chill (DC) cast
erogeneous nucleation of solidication of one phase
[1, 2, 4] to produce ingots which are subsequently
by another. Early work [1519] concentrated on the
worked to shape. Variations in both solidication
monotectic systems AlIn, AlCd, AlPb, AlSn
velocity and cooling rate across the cross-section of
and PbCu. In these systems the components were
the ingot during casting can alter the secondary
mutually immiscible, facilitating the study of the
phase content, size and morphology with position
heterogeneous nucleation of solidication of In, Cd,
in the ingot, by changing the nucleation and growth
Pb and Sn droplets dispersed in an Al or Cu
mechanisms that predominate locally [3]. Following
matrix. The eect of impurities in the form of delib-
casting, the outermost part of the ingot is com-
erate ternary additions of Fe, Si, Mg, Zn, Cu, Mn,
monly scalped o to remove the uneven cast surface
Ga and Ge, on the solidication of droplets was
and inverse segregation zone. In surface-critical ap-
also investigated [2025]. These ternary additions
plications, however, the remaining material often
were miscible both in the droplets and in the
has to be homogenised by heat treatment, as vari-
matrix. As a further step towards modelling hetero-
ations in phase content have to be minimised to
geneous nucleation of secondary phases in commer-
produce an even response to surface etchants and
cial alloys, the nucleation of eutectic Al2Cu and
anodising in the nal gauge.
eutectic Si droplets in AlCu and AlSi alloys, re-
There has been considerable study of the growth
spectively, and the eect of ternary impurity ad-
behaviour of secondary phases in Al alloys using
ditions (e.g. P) on the nucleation behaviour were
studied [2630]. The heterogeneous nucleation of
{To whom all correspondence should be addressed. Al, an important process in the consideration of
4387
4388 ALLEN et al.: NUCLEATION OF SECONDARY PHASES

grain renement, was also investigated by studying
the solidication of Al droplets in a Zr aluminide
matrix [31].
These techniques have been used recently to
study the impurity-catalysed nucleation of second-
ary phases in 1xxx Al alloys [3234]. The purpose
of the present paper is to describe a detailed study
extending this work, concentrating on the eect of
V and grain rener additions. Melt spinning was
used to produce a dispersion of submicron second-
ary phases in a higher melting point Al matrix,
which were then melted to form entrained eutectic
liquid droplets in a solid Al matrix prior to cooling
and resolidication. As the droplets were dispersed,
each individual droplet required its own nucleant
for solidication, i.e. by dividing the liquid into
droplets the degree of nucleation control on second-
ary phase selection was greatly exaggerated over
that of growth. The resolidication of the droplets,
and the eect of impurities on secondary phase
nucleation was studied using DSC. Nucleation is
one important factor that inuences secondary
phase selection during the nal 1015% of solidi-
cation during industrial casting processes also,
where a proportion of the remaining liquid becomes
pinched-o into puddles between the Al dendrite
arms prior to solidication.
2. EXPERIMENTAL
A series of high purity-based Al0.3 wt% Fe
0.1 wt% Si alloys consisting of >99.995 wt% pure
Al, Fe and Si, with various additions of V, Si and
Al5 wt% Ti, Al5 wt%Ti1 wt% B, Al3 wt%
Ti1 wt% B, Al2.2 wt% Ti1 wt% B, Al2.2 wt%
B and Al5 wt% Ti0.02 wt% C grain reners
were manufactured by melting the components in a
resistance furnace then casting into steel moulds.
The high purity alloys were compared with a lower
purity Al0.3 wt% Fe0.1 wt% Si alloy prepared
from a commercial purity Al base containing
2500 ppm of impurities, originating from the
smelting process, with a 1:1000 addition (by weight)
of Al3 wt% Ti1 wt% B grain rener alloy. All
alloy compositions were determined by spark emis-
sion spectrographic analysis, in each case as the
mean of three analyses, and are listed in Table 1.
Samples of 25 g each of the high purity alloys and
the lower purity alloy were rapidly remelted in a
4
quartz crucible under Ar at 4.5  10 Pa and melt-
spun when at a temperature >8008C by ejection
through a 1 mm nozzle using an Ar overpressure of
4
1.5  10 Pa on to a Cu wheel rotating at 23 m/s.
Two high purity alloys with combined additions of
V and AlTiC grain rener were also melt-spun
when at other temperatures <8008C. All resulting
ribbons were typically 0.11 m long, <5 mm wide
and 50150 mm thick.
Specimens of 22 mg from each ribbon were
sealed into either W- or Mo-lined Cu pans and ana-
lysed in either a TA Instruments 2010 DSC or a
MettlerToledo 821e DSC, using an identically pre-
pared W- or Mo-lined empty Cu pan as a reference.
Two cycles of partial melting and resolidication,
i.e. eutectic melting and resolidication of the sec-
ondary phase particles only, were performed under
a dynamic Ar atmosphere, by heating from 632 to
6588C at 2 K/min, resolidifying at 2 K/min to
6328C, and then remelting and resolidifying once
more in an identical manner.
Solidication microstructures were investigated
by quenching DSC specimens from some of the rib-
bons in contact with a water-cooled steel block at
dierent stages during resolidication after partial
melting. Specimens were quenched from: (i) the
highest temperature T experienced during partial
melting; (ii) an intermediate temperature I just after
the rst major resolidication peak; (iii) an end
temperature E immediately after all the major reso-
lidication peaks; and (iv) 25008C, well below all

Table 1. Alloy compositions

Composition
Base alloys Fe (wt%) Si (wt%) V (ppm) Ti (ppm) B (ppm)

a
Lower purity 0.3 0.1 100 50 10
High purity 0.32 0.11

Additions to high purity base Fe (wt%) Si (wt%) V (ppm) Ti (ppm) B (ppm)

Low V(III) 0.32 0.11 14
Low V(II) 0.32 0.11 68
Low V 0.32 0.11 125
High V 0.32 0.11 560
AlTiCb 0.32 0.11 100
Al2.2Ti1B 0.32 0.11 25 11
Al5Ti1B 0.32 0.11 49 8
Low V + AlTi 0.32 0.11 57 26
Low V + AlTiCb 0.31 0.11 130 100
Low V + Al2.2Ti1B 0.31 0.11 67 25 10
Low V + Al5Ti1B 0.32 0.11 125 41 8
Low V + AlB 0.31 0.11 151 21

a
Lower purity alloy based on >99.95 wt% pure starting stock. All other alloys based on >99.995 wt% pure starting stock.
b
C levels in AlTiC and low V + AlTiC alloys were not measured.
 ALLEN et al.: NUCLEATION OF SECONDARY PHASES 4389

Table 2. Summary of quench experiments

Quench point temperatures (8C) and designations

Ribbon T: end of partial melting I: between 1st E: after end of 25008C fully
and 2nd peaks major peak solid

Lower purity 647.9 640.9

High purity 655.8 646.1 2500
High V 647.1 641.9
Low V + Al5Ti1B 656.6 648.0 641.4 2500

the major resolidication peaks, i.e. when the
microstructure was fully solid. The ribbons investi-
gated and the exact quench temperatures used in
each case are summarised in Table 2.
Quenched specimens were mounted, ground, and
then polished using colloidal silica. Specimens were
then examined in an ISI DS130 SEM operating at
1020 kV. Quenched specimens were also ion
beam-thinned and examined in a JEOL 2000FX
TEM operating at 200 kV. To assist in secondary
phase identication, particles were extracted by dis-
solving the Al matrix in boiling butanol under
pressure [3539], mounted on an amorphous C lm
and analysed using selected area diraction pattern
(SADP) analysis and electron microprobe analysis
(EPMA) using an energy dispersive X-ray (EDX)
LINK AN10000 detector on the JEOL 2000FX
TEM. The distribution of the chemical elements Al,
Fe, Si, V and Ti between the primary Al matrix
and the secondary phase particles was examined
using both a wavelength dispersive X-ray (WDX)
microprobe analyser on a JEOL 733 ``Superprobe''
and an EDX detector on the ISI DS130 SEM.
Specimens analysed for Si content were polished

Table 3. Melting and solidication onset and peak temperatures

Partial melting Resolidication

Ribbon First First Second Second First First Second Second

melting melting melting melting solidication solidication solidication solidication
onset peaks onset peaks onset peaks onset peaks
(8C) (8C) (8C) (8C) (8C) (8C) (8C) (8C)

Lower purity 650.9 653.8 649.2 651.5 652.8 651.6 653.2 651.7
655.2 655.0 645.3 645.3
642.0 642.2
High purity 650.0 653.4 651.2 654.5 652.8 651.4 653.2 651.6
654.8 639.5 640.0
Low V(III) 650.5 653.0 650.4 654.1 652.2 650.8 652.4 650.9
654.5 638.9 639.6
650.7 652.2 651.0 654.4 652.4 650.9 652.8 651.3
654.7 640.0 640.5
Low V(II) 650.2 652.9 650.7 654.3 652.3 650.8 652.8 651.1
654.5 639.9 640.8
650.9 653.1 651.1 654.5 652.0 650.9 652.6 651.2
655.2 640.5 641.0
650.7 653.1 651.1 654.3 653.0 652.1 653.3 652.0
654.9 640.2 641.2
Low V 650.3 652.9 650.6 654.1 652.2 650.7 652.5 650.9
654.5 640.0 640.3
650.5 653.3 651.4 654.4 652.9 651.2 653.9 652.5
654.9 639.5
High V 651.0 653.5 649.4 651.4 652.9 651.4 653.1 651.6
655.3 655.1 644.7 644.8
650.7 653.9 649.5 651.3 652.6 651.4 652.7 651.4
655.7 655.3 644.8 644.8
AlTiC 650.2 653.3 650.7 654.2 652.5 651.0 652.6 651.0
654.6 638.3
Al2.2Ti1B 650.6 653.1 649.2 650.0 652.6 651.9 652.7 650.9
654.7 654.2 639.3 639.2
Al5Ti1B 649.7 652.7 648.7 649.6 652.6 651.9 652.7 651.4
654.4 653.8 639.6 640.1
Low V + AlTi 651.0 653.2 649.7 650.4 652.8 651.9 653.2 651.4
654.7 654.4 640.9 641.1
Low V + AlTiC 650.8 653.4 649.6 650.7 652.6 651.1 653.1 651.5
655.3 654.7 640.5 640.9
Low V + Al2.2Ti1B 650.7 653.2 649.1 650.6 652.9 652.1 652.3 651.3
654.9 654.3 644.6 643.9
Low V + Al5Ti1B 650.5 652.8 648.7 650.6 652.3 651.7 652.3 651.3
654.4 654.3 644.1 643.9
Low V + AlB 650.6 653.1 649.3 651.4 653.1 652.2 653.6 651.9
655.1 654.9 644.9 645.6
4390 ALLEN et al.: NUCLEATION OF SECONDARY PHASES

Fig. 1. (caption opposite).

 ALLEN et al.: NUCLEATION OF SECONDARY PHASES 4391

Fig. 1. (a) Melting endotherms from high purity base, high purity + V, high purity + V + Al5Ti1B
and lower purity ribbons. (b) Resolidication exotherms from high purity base, high purity + V, high
purity + V + Al5Ti1B and lower purity ribbons after partial melting. (c) Remelting endotherms
from high purity base, high purity + V, high purity + V + Al5Ti1B and lower purity ribbons after
partial melting and resolidication.

using a 1 mm diamond suspension prior to analysis,
to avoid introducing contamination from the col-
loidal Si polishing stage.
3. RESULTS
3.1. DSC
Figure 1(a) shows typical rst-cycle partial melt-
ing DSC endotherms, which all consisted of a doub-
let with a melting onset temperature in the range of
649.7651.08C. Figure 1(b) shows typical rst-cycle
resolidication DSC exotherms after partial melt-
ing, which all consisted of a large peak with a soli-
dication onset temperature in the range of 652.0
653.18C, followed in the cases of the high purity
ribbons by a smaller peak at a lower temperature.
The exotherm from the lower purity ribbon con-
tained two smaller peaks at lower temperature,

Table 4. Solidication onsets of the minor peaks AQ (where determined)

Ribbon Peak Onset temperature (8C): Onset temperature (8C):

1st resolidication 2nd resolidication

Lower purity A 647.3 647.0

B 642.6 642.9
High purity C 643.9
Low V(III) D 642.3
Low V(II) E 641.5 642.0
Low V F 641.7 641.2
High V G 646.1 646.1
AlTiC H 641.4
Al2.2Ti1B J 640.7 640.0
Al5Ti1B K 640.7 641.1
Low V + AlTi L 642.5 642.6
Low V + AlTiC M 641.8 642.2
Low V + Al2.2Ti1B N 646.9 646.0
Low V + Al5Ti1B P 645.5 644.9
Low V + AlB Q 647.4 648.2
4392 ALLEN et al.: NUCLEATION OF SECONDARY PHASES
denoted A and B. Table 3 lists rst- and second-
cycle melting and solidication onset and peak tem-
peratures from partial melting and resolidication
of all the melt-spun ribbons investigated, as listed
in Table 1. Table 4 lists the onset temperatures of
all the smaller peaks observed at lower temperature
on rst- and second-cycle solidication, denoted A
Q, which varied with ribbon composition in the
range 640.7647.48C.
Figure 1(c) shows typical second-cycle partial
melting DSC endotherms after partial melting and
resolidication, which all consisted of a large single
peak with a melting onset temperature in the range
of 650.4651.48C, similar to the melting onset tem-
perature on rst-cycle melting, which was in the
range of 649.7651.08C, and in the same position as
the doublet detected in the rst-cycle partial melting
endotherms. The endotherms from the lower purity
ribbon, and from the high purity ribbon containing
either high V (560 ppm), grain rener (excluding
AlTiC), or low V (57151 ppm) plus grain rener
also contained a smaller single peak at a melting
onset temperature 21.52 K lower, in the range
648.7649.78C. Figure 1(c) shows this peak in the
cases of the lower purity ribbon, labelled T, and the
high purity ribbons containing high V (560 ppm),
and low V plus AlTiB grain rener, labelled R
and S, respectively. The size of this smaller single
peak in the second-cycle partial melting DSC
endotherms from the high purity ribbon containing
low V plus AlTiC grain rener increased with
decreasing melt-spinning temperature in the range
7108008C, from virtually absent at 8008C to a
similar size to that from the low V plus AlTiB
grain rener at 27108C.
Increasing the Si content of the high purity base
ribbon from 0.1 wt% to 0.2 wt% broadened the
double melting peak observed in the rst-cycle melt-
ing endotherm and depressed its melting onset to
648.38C. These eects have been previously
explained to be due to the gradients of the ternary
AlFeSi liquidus and solidus surfaces [34]. A smal-
ler single peak prior to the main melting peak was
also observed in the second-cycle melting
endotherm from the Al0.3 wt% Fe0.2 wt% Si
ribbon, which had only been present in the corre-
sponding endotherm from the Al0.3 wt% Fe
0.1 wt% Si ribbon on the addition of sucient V or
grain rener [see Fig. 1(c)].
A similar double melting peak was also observed
in the rst-cycle melting endotherms from the high
purity Al0.3 wt% Fe0.1 wt% Si alloy in the as-
mould-cast condition, with two additional smaller
peaks at lower temperature. These smaller peaks
were absent in the second melting endotherm, and
the double peak had become a single peak, in a
manner analogous to that seen in the endotherms
from the melt-spun ribbons [cf. Figs 1(a) and (c)].
In other words, decreasing the solidication rate
(from melt spinning to mould casting) introduces
smaller peaks on rst melting, although on remelt-
ing following solidication at 2 K/min in the DSC
these smaller peaks are again absent.
The second-cycle resolidication DSC exotherms
from all ribbons were all similar to the rst-cycle
resolidication exotherms as shown in Fig. 1(b),
and again consisted of a large peak with a solidi-
cation onset temperature in the range of 652.4
653.98C, followed in the case of the high purity rib-
bons by a smaller peak at a lower temperature, the
same as was observed on rst-cycle resolidication
after partial melting. The exotherm from the lower
purity ribbon contained two smaller peaks at lower
temperature, again the same as were observed on
rst-cycle resolidication. The solidication onset
temperatures of all these smaller peaks varied with
ribbon composition in the range of 640.0648.28C
as listed in Table 4.
3.2. Microscopy
3.2.1. EDX analysis of extracted particles. Figures
2(a) and (b) show EDX analyses from secondary
phase particles extracted from the high purity base
ribbon and the low V (125 ppm) plus Al5Ti1B
grain rener ribbon, respectively. Samples of both
ribbons were quenched from temperature E (refer
to Table 2), i.e. after completion of all major solidi-
cation peaks as detected by DSC. The ranges of Si
and Fe contents of the secondary phase particles
extracted from the high purity base ribbon [Fig.
2(a)], the high V (560 ppm) ribbon, the low V
(125 ppm) plus Al5Ti1B grain rener ribbon
[Fig. 2(b)] and the lower purity ribbon are summar-
ised in Table 5. In all analyses the only elements
detected were Al, Fe or Si. The ranges of Fe con-
tents of the particles extracted from all the ribbons
analysed were similar, in the range 1330 at.% Fe.
The ranges of Si contents from the high V ribbon,
from the low V plus Al5Ti1B grain rener ribbon
and from the lower purity ribbon were all similar,
in the range 05 at.% Si. The range of Si contents
from particles extracted from the high purity base
ribbon was higher, in the range 18 at.% Si.
3.2.2. Particle identications by SADP analysis of
extracted particles. In Figs 2(a) and (b) solid circles
indicate particles that were suciently thin to be
identied by SADP analysis.
3.2.2.1. High purity base ribbon. Particle B1 [Fig.
2(a)] was identied by SADP analysis to be the
equilibrium Fe aluminide Fe4Al13 [40]. Figure 3
shows a bright eld TEM micrograph of particle B2
[Fig. 2(a)]. Particle B2 could not be identied from
SADP analysis as any known Fe aluminide (e.g.
Fe4Al13, FeAl6 or FeAlm) or more Si-rich phase
(e.g. a-AlFeSi, b-AlFeSi or Si). This indicates that
more than one type of phase is present in the high
purity base ribbon when quenched from tempera-
ture E.
3.2.2.2. High V ribbon. Figures 4(a) and (b) show
a bright-eld TEM micrograph and SADP from a
 ALLEN et al.: NUCLEATION OF SECONDARY PHASES 4393

Fig. 2. (a) EDX analyses from particles extracted from high purity ribbon quenched from point E (see
Table 2). Solid circles represent particles identied by SADP analysis. Note that the horizontal scale is
not the same as in (b). (b) EDX analyses from particles extracted from low V + Al5Ti1B grain re-
ner ribbon quenched from point E (see Table 2). Solid circles represent particles identied by SADP
analysis.
4394 ALLEN et al.: NUCLEATION OF SECONDARY PHASES

Table 5. Fe and Si content ranges from extracted secondary phase particle labelled G4 in Fig. 2(b), containing 19 at.%
particles
Fe and a higher Si content of 3.8 at.% Si, was
Ribbon Fe content range Si content range identied as FeAlm, with double diraction spots
(at.%) (at.%) along {hh0} corresponding to {110} stacking faults
[41], similar to the high Si particle extracted from
Lower purity 15.129.6 03.1
High purity 14.526.4 08.2 the high V alloy as shown in Fig. 5(a). Particles G2
High V 12.827.4 0.54.6 and G3, containing 3.2 at.% Si and 3.4 at.% Si, re-
Low V + Al5Ti1B 18.030.0 1.14.0
spectively, were also identied as FeAlm.
3.2.2.4. Lower purity ribbon. An extracted par-
particle containing 24 at.% Fe and 0.7 at.% Si ticle containing 24.5 at.% Fe and 0.8 at.% Si was
extracted from the high V ribbon. The SADP was identied as Fe4Al13, with spot streaking in the
indexed as corresponding to the equilibrium Fe alu- SADP corresponding to stacking faults on {001}
minide Fe4Al13 [40]. Spot streaking along {001} [40], similar to that observed in the SADPs from
directions in reciprocal space indicated that the the low Si particle extracted from the high V ribbon
Fe4Al13 particle contained {001} stacking faults and the particle labelled G1 in Fig. 2(b). Six other
[40], which can be seen in the bright eld micro- particles containing Si contents between 0.6 at.% Si
graph. Another particle containing 1.4 at.% Si was and 2.3 at.% Si were also identied as Fe4Al13.
also identied as Fe4Al13. Figures 5(a) and (b) show
a bright-eld TEM micrograph and corresponding
SADP from a particle containing 22 at.% Fe and a
higher Si content of 2.7 at.% Si extracted from the
high V ribbon. The SADP was indexed as corre-
sponding to the metastable Fe aluminide FeAlm
[41]. Double diraction spots along {hh0} directions
in reciprocal space indicated that the FeAlm particle
contained {110} stacking faults [41], which can just
be seen in the thinnest region of the particle in the
bright-eld micrograph. Other particles containing
4.2 at.% Si and 4.5 at.% Si were also identied as
FeAlm.
3.2.2.3. Low V plus Al5Ti1B grain rener rib-
bon. The particle labelled G1 in Fig. 2(b), contain-
ing 22 at.% Fe and 1.4 at.% Si, was identied as
Fe4Al13, with spot streaking also being observed in
the SADP corresponding to stacking faults on
{001} [40], similar to the low Si particle extracted
from the high V ribbon as shown in Fig. 4(a). The

Fig. 4. (a) Transmission electron micrograph of low Si

Fig. 3. Transmission electron micrograph of high Si con-
tent particle B2, extracted from high purity ribbon,
quenched from point E (see Table 2).
content particle extracted from high V ribbon, quenched
from point E (see Table 2), showing {001} stacking faults.
(b) Selected area diraction pattern from particle in (a),
showing streaking along {001} directions (where h and l
are integers).
 ALLEN et al.: NUCLEATION OF SECONDARY PHASES 4395

Fig. 5. (a) Transmission electron micrograph of higher Si content particle extracted from high V ribbon,
quenched from point E (see Table 2). Stacking faults parallel to {110} are just visible in the thinnest
region of the particle. (b) Selected area diraction pattern from the particle in (a) (where l=2n, and n
and h are integers). Open circles are double diraction spots.
4396 ALLEN et al.: NUCLEATION OF SECONDARY PHASES

3.2.3. Solidication microstructures. Figure 6(a)
shows a typical backscattered electron image (BEI)
of the high purity base ribbon quenched from the
highest temperature T (Table 2) before any second-
ary phase resolidication took place. The micro-
structure consisted of equiaxed Al cells, with Fe-
rich secondary phases on the cell boundaries and
within the cells, and a precipitate-free zone either
side of the cell boundaries. Figures 6(b) and (c)
show higher magnication secondary electron
images (SEIs), indicating the ne-scale eutectic
microstructure of the secondary phases both at the

Fig. 6. (caption opposite).

 ALLEN et al.: NUCLEATION OF SECONDARY PHASES 4397

Fig. 6. Scanning electron micrographs of high purity ribbon quenched from point T (see Table 2): (a)
low magnication view (backscattered mode); (b) cell-boundary phases with ne quenched-in eutectic
structure, indicating that they were liquid at the point of quench. These are the sites of Fe4Al13 for-
mation during cooling at 2 K/min (secondary mode); (c) intracellular phases also with ne quenched-in
eutectic structure, indicating that they were also liquid at the point of quench. These are the sites of
entrained liquid puddles that undercool at 2 K/min (secondary mode).

cell boundaries and intracellularly. This indicates
that all secondary phases solidied rapidly, i.e. that
they were liquid prior to the point of quench.
When the high purity base ribbon was quenched
from temperature E [Table 2], after the major reso-
lidication peak [as shown in Fig. 2(a)], the cell
boundary phases were blockier and more faceted
than when quenched from temperature T, before
the major resolidication peak. This indicated that
the cell boundary phases solidied during the major
resolidication peak. The intracellular phases
retained the ne-scale eutectic structure indicating
they were still liquid after the end of the major
resolidication peak.
Figure 7 shows a typical BEI of the intracellular
phases in the high purity base ribbon quenched
from a temperature of 25008C, well below the
major resolidication peak observed by DSC. The
intracellular secondary phases were blockier and
more faceted than when quenched from tempera-
ture E, just after the major resolidication peak.
This indicated that in the high purity base ribbon
the intracellular phases undercooled and resolidied
at temperatures below the end of the major resolidi-
cation peak. This resolidication is just detected
by DSC as the broad, indistinct exotherm labelled
C in Fig. 1(b).
The correspondence of the major resolidication
peak to the solidication of secondary phases at the
cell boundaries was also observed in the high V rib-
bon, the low V plus Al5Ti1B grain rener ribbon,
and the lower purity ribbon. Figure 8 shows a
TEM micrograph of an in situ intracellular phase
from the lower purity ribbon quenched from tem-
perature I (Table 2), i.e. after the major resolidica-
tion peak, but before peaks A and B [Fig. 1(b)].
Figure 8 shows the ne structure present in the in-
tracellular phase, indicating that it was an isolated
droplet of liquid prior to the point of quench.
The intracellular phases in the high V ribbon, the
low V plus Al5Ti1B grain rener ribbon, and the
lower purity ribbon quenched from temperature E,
i.e. below the end of peaks G, P and B, respectively
[Fig. 1(b)], were blockier and more faceted than
when quenched from temperature I, above the
onset of peaks G, P and A, respectively. The par-
ticle morphologies were more similar to those seen
in the high purity base ribbon when quenched from
25008C (Fig. 7). Peaks G, P, A and B therefore
correspond to the solidication of the intracellular
secondary phases.
3.2.4. Distribution of elements in the solidication
microstructures. Both WDX/EPMA and EDX ana-
lyses of SEM bulk specimens, and EDX analyses of
TEM foils, indicated that none of these techniques
were able to detect readily either V in the ribbons
containing R125 ppm V, or Ti in ribbons containing
grain rening additions of R1:1000 addition level.
Figures 9(a) (d) show the EPMA Fe, Si, Ti and
V maps, respectively, of an Al cell in a high V plus
4398 ALLEN et al.: NUCLEATION OF SECONDARY PHASES

Fig. 7. Secondary electron micrograph of intracellular phases in high purity ribbon quenched from
25008C, with blockier morphology.

10:1000 Al3Ti1B ribbon partially melted, resolidi- corresponding to the large single peak common to
ed and quenched from temperature I, i.e. from in all exotherms on rst- and second-cycle resolidica-
between the two peaks detected by DSC. Both Fe tion after partial melting, with a solidication onset
and Si were spatially associated with the cell bound- temperature in the range of 652.0653.18C [Fig.
ary and intracellular secondary phases, consistent 1(b)] and 652.3653.98C, respectively. The for-
with the Fe and Si detected in the EDX data from mation of the equilibrium Fe4Al13 phase as the ma-
extracted particles. V was detected, and was segre- jority phase on resolidication at 2 K/min is to be
gated away from the Al cell boundaries and Fe alu-
minide particles. Ti was distributed in small
particles whose locations were dierent from the Fe
aluminide particles. Assuming that any TiAl3 par-
ticles present in the Al3Ti1B master alloy will
have dissolved on alloying with the high purity
base, the Ti distribution observed suggests that the
discrete locations of Ti correspond to a distribution
of insoluble TiB2 particles.

4. DISCUSSION

As shown in Fig. 1(a), the rst-cycle partial melt-

ing behaviour of all ribbons of a given Fe and Si
content is essentially the same, irrespective of trace
composition. Variations in trace chemistry do not
alter signicantly, therefore, the secondary phase
contents that result after any equilibration of the
melt-spun microstructures during heating in the
DSC.

4.1. Fe4Al13 solidication and remelting on Al cell

boundaries Fig. 8. Transmission electron micrograph of intracellular
phase in commercial purity ribbon, quenched from point I
SADP analysis showed that Fe4Al13 was formed (see Table 2). Fine quenched-in eutectic structure indicates
in all ribbons analysed, as illustrated in Fig. 4(a), that it was liquid at point of quench.
 ALLEN et al.: NUCLEATION OF SECONDARY PHASES 4399

Fig. 9. (a)(d) Fe, Si, Ti and V maps of a high purity ribbon containing a combined addition of
585 ppm V and 10:1000 Al3 wt% Ti1 wt% B quenched from point I (see Table 2). Fe and Si are seg-
regated to the secondary aluminide phases, V is segregated to the Al. The distribution of Ti does not
correlate with the distribution of the (Fe, Si) aluminides, nor with that of V, and indicates the distri-
bution of TiB2 particles originating from the grain rener master alloy addition. The TiAl3 particles
present in the master alloy will have been dissolved following addition of the master alloy to the high
purity base alloy.

anticipated given the relatively slow cooling rate [4].
Comparison of microstructures quenched from
before and after the Fe4Al13 resolidication peak
shows that Fe4Al13 solidication occurs predomi-
nantly on the Al cell boundaries. Remelting of the
Fe4Al13 is detected as the large single peak common
to all second-cycle melting endotherms [Fig. 1(c)].
4.2. Intracellular liquid droplet solidication and
remelting in the absence of impurities
The resolidication behaviour of the intracellular
liquid droplets depends upon the trace chemistry of
the ribbon. In the high purity base ribbon the liquid
droplets undercool to temperatures below the end
of the Fe4Al13 resolidication peak. The resolidica-
4400 ALLEN et al.: NUCLEATION OF SECONDARY PHASES
tion of the liquid droplets at 2 K/min is just
detected by DSC as the broad, indistinct exotherm,
labelled C in Fig. 1(b). Only Fe4Al13 is detected on
remelting, however, as shown in Fig. 1(c), indicating
that the liquid droplets solidify at 2 K/min either as
Fe4Al13 or as a metastable phase which rapidly
transforms to Fe4Al13 on reheating prior to remelt-
ing. EDX data from particles extracted following
quenching (at 2300 K/min), Fig. 2(a) indicate that
phases with a higher Si content than Fe4Al13 can
indeed form. The morphology of one such phase as
observed by TEM [Fig. 6(a)] suggests that these
higher Si content phases form within entrained
liquid droplets that can reach higher undercoolings
than the liquid at the cell boundaries. These phases,
however, rapidly transform to Fe4Al13 on reheating
and consequently only Fe4Al13 is detected on
remelting.
4.3. Intracellular liquid droplet solidication and
remelting in the presence of impurities
4.3.1. FeAlm solidication and remelting in
entrained liquid droplets. On the basis of mor-
phology, Fe4Al13 and FeAlm cannot be readily dis-
tinguished in dilute Al alloys. On the basis of
SADP analysis, the EDX data from particles
extracted from the high V ribbon, the low V plus
Al5Ti1B grain rener ribbon, and the lower of the ribbon in each case.
purity ribbon can be divided into two groups: Si
contentR22.7 at.% Si and > 22.7 at.% Si, corre-
sponding to Fe4Al13 and FeAlm particles, respect-
ively. The mean composition of group I is 22.0 at.%
Fe, 1.3 at.% Si (quoted to the nearest 0.5 at.% Fe
and 0.1 at.% Si), which correlates well with the
value of 22.5 at.% Fe, 1.5 at.% Si calculated from
published values for Fe4Al13 in DC-cast alloys of
similar bulk Si content [2, 4244]. Stacking faults
on {001} and associated spot streaking along {001}
in reciprocal space from the SADPs of particles in
group I [Fig. 4(a)] are also characteristic of Fe4Al13
[40]. The mean composition of group II is 19.5 at.%
Fe, 3.4 at.% Si, which correlates well with the value
of 18.0 at.% Fe, 3.1 at.% Si calculated from pub-
lished values for FeAlm in DC-cast alloys of similar
bulk Si content [2, 4244]. Stacking faults on {110}
and associated double diraction spots along {hh0}
in reciprocal space from the SADPs of particles in
group II [Fig. 5(a)] are also characteristic of FeAlm
[41].
FeAlm forms as a minority phase on resolidica-
tion at 2 K/min after partial melting of the high V
ribbon, the low V plus Al5Ti1B grain rener rib- alloys is well documented [13]. In the lower purity
bon, and the lower purity ribbon. The FeAlm resoli-
dication corresponds to the smaller single peaks
G, P and A, respectively, in Fig. 1(b), with a solidi-
cation onset temperature in the range of 644.9
647.38C. This peak follows the large resolidication
peak of Fe4Al13 common to all resolidication exo-
therms [Fig. 1(b)]. The peak labelled B in the resoli-
dication exotherms from the lower purity ribbon
has been previously attributed to be due to the pre-
sence of trace levels (23 ppm) of phosphorus [32].
The phase to which this peak corresponds remains
to be identied, however.
Comparison of microstructures quenched from
before and after the FeAlm resolidication peak
shows that FeAlm solidication occurs predomi-
nantly within the Al cells. Remelting of the FeAlm
is detected, prior to the remelting of the Fe4Al13, as
a small single peak labelled R, S and T in the sec-
ond-cycle melting endotherms from the high V rib-
bon, the low V plus Al5Ti1B grain rener ribbon
and the lower purity ribbon, respectively, as shown
in Fig. 1(c), with a melting onset temperature in the
range of 648.7649.78C. The metastability of the
FeAlm phase has been previously conrmed by iso-
thermal holding in the solid state prior to remelting
[34], which reduces the area of the subsequent
FeAlm melting peak.
The FeAlm remelting peak is also detected in the
second-cycle melting endotherms from the ribbons
containing grain rener (excluding AlTiC), and
low V (57151 ppm) plus grain rener. The smaller
peaks present in the resolidication exotherms from
these ribbons therefore also correspond to the reso-
lidication of the FeAlm phase, the solidication
onset temperature varying with the trace chemistry
4.3.2. Formation of other phases on solidication
and remelting of entrained liquid droplets. FeAlm is
not formed in the low V (R125 ppm), and AlTiC
grain rener ribbon. The smaller peaks present in
the resolidication exotherms from these ribbons
therefore correspond either to the solidication of
undercooled Fe4Al13 or of a metastable phase
which rapidly transforms to Fe4Al13 on reheating
prior to remelting as was the case for the high
purity base ribbon (Section 4.2). One such phase
may be the other common metastable AlFe eutec-
tic, FeAl6. A number of workers [45] have noted
that FeAl6 rapidly transforms to Fe4Al13 at tem-
peratures just below the eutectic temperature, and
that the presence of Si accelerates this transform-
ation.
4.4. FeAlm formation
4.4.1. Combined action of V plus AlTiB grain
rener in lower purity ribbon. The occurrence of
FeAlm during DC casting of commercial purity
ribbon 2100 ppm V promotes the formation of
FeAlm. However, in high purity ribbon 2500 ppm
V is necessary [32]. The addition of AlTiB grain
rener to this ribbon promotes FeAlm formation at
V levels of 2100 ppm. The presence of AlTiB
grain rener in the lower purity ribbon therefore
acts in conjunction with the V present to promote
FeAlm formation.
 ALLEN et al.: NUCLEATION OF SECONDARY PHASES
4.4.2. Combined action of V plus AlTiC grain
rener and eect of melt-spinning temperature. The
size of the peak attributed to the melting of FeAlm
observed in the second-cycle melting endotherm
when Al5Ti1B grain rener is added to the low V
ribbon is much larger than when AlTiC grain
rener is added. Under identical melt-spinning con-
ditions, therefore, less FeAlm forms in ribbons con-
taining V plus AlTiC than V plus AlTiB. The
amount of FeAlm that forms in the V plus AlTiC
grain rener alloy increases, however, as melt-spin-
ning temperature decreases, as reported in Section
3.1. The sensitivity of FeAlm formation to the melt
superheat experienced during processing is similar
to the sensitivity of primary grain renement by
AlTiC [46,47] to casting temperature, suggesting
that the amount of FeAlm formed may be linked to
the as-solidied primary grain size. However, other
results discussed below (Section 4.4.3) indicate that
primary grain renement does not play a role in the
promotion of FeAlm.
4.4.3. Eect of Ti:B ratio in AlTiB grain re-
ner. The size of the peak attributed to the melting
of FeAlm observed in the second-cycle melting
endotherm when Al5Ti1B grain rener is added
to the low V ribbon is similar to that when Al
2.2Ti1B grain rener is added, i.e. the amount of
FeAlm formed does not change signicantly with
Ti:B ratio. For eective primary grain renement
by AlTiB addition, however, a stoichiometric
excess of Ti is necessary [48]. The insensitivity of
FeAlm formation to Ti:B ratio therefore suggests
that the amount of FeAlm formed is not linked to
the as-solidied primary grain size.
4.4.4. Grain size in partially melted and resolidied
ribbons. Comparison of grain sizes in microstruc-
tures quenched prior to FeAlm formation following
partial melting and resolidication indicates that
any grain size dierences that exist with ribbon
composition prior to partial melting are removed
by grain coarsening in the partially molten state
[49]. This also indicates that the amount of FeAlm
formed is not linked to the as-melt-spun primary
grain size.
4.4.5. Role of direct nucleation by grain rener
particles. The size of the peak attributed to the soli-
dication of FeAlm observed in the rst-cycle resoli-
dication exotherm when Al5Ti1B grain rener is
added to the low V ribbon is similar to that when
AlB grain rener is added. The promotion of
FeAlm by AlB, AlTiB (Section 4.4.1) and Al
TiC additions (Section 4.4.2) shows that the
chemical identity of the grain rener in the pro-
motion of FeAlm is unimportant. This suggests that
FeAlm is not directly nucleated either by the corre-
sponding grain rener particles (AlB2, TiB2 or TiC,
respectively) or some reaction product between V
and the grain rener particles. Further evidence
that FeAlm is not directly nucleated by the grain
rener particles is provided by the results of chemi-
4401
cal analyses of quenched liquid droplets. No Ti was
detected in the Fe aluminides in AlTiB grain re-
ner containing alloys [cf. Figs 9(a) and (c)]. AlTi
B grain reners have been shown to contain two
types of Ti-rich particles, TiAl3 and TiB2 [48]. The
small Ti-containing particles shown in Fig. 9(d) are
thought to be TiB2 particles that originate from the
grain rener addition, as TiAl3 particles are known
to become unstable and dissolve when added to di-
lute Al alloys [48]. Thus TiB2 particles do not
appear to be associated with the Fe aluminides in
the microstructure, contrary to the proposals of
previous workers [4, 5052]. WDX analysis shows
that V is partitioned into the Al matrix [Fig. 9(d)],
away from the Fe aluminides during partial melt-
ing, as would be expected from the peritectic nature
of the AlV binary phase diagram. However, given
the slow diusion of V in solid Al, this may provide
a mechanism for concentrating V in a shell sur-
rounding the entrained liquid puddle. The width of
this shell would probably be too narrow to be
detected by EPMA techniques applied to bulk spe-
cimens.
4.5. Role of interdendritic liquid composition
4.5.1. Importance of bulk Si content. The presence
of a smaller single peak at a lower melting onset
temperature than the larger single peak in the sec-
ond-cycle melting endotherm from the high Si Al
0.3 wt% Fe0.2 wt% Si ribbon, as reported in Sec-
tion 3.1, indicates that increasing the Si level from
0.1 wt% to 0.2 wt% promotes the formation of
FeAlm during resolidication after partial melting.
This indicates that in alloys of a suciently high Si
content neither V nor grain rener is a prerequisite
for FeAlm formation.
4.5.2. Importance of solidication rate. The pre-
sence of two smaller single peaks at lower melting
onset temperatures than the larger double peak in
the rst-cycle melting endotherm from the as-
mould-cast Al0.3 wt% Fe0.1 wt% Si alloy, as
reported in Section 3.1, indicates that metastable
phases (i.e. including FeAlm) form during mould
casting, even in the absence of V and grain rener,
and do not subsequently fully transform to Fe4Al13
during heating in the DSC. These metastable phases
form due to the higher solidication rate experi-
enced during mould casting compared to during
controlled cooling at 2 K/min in the DSC, explain-
ing their removal following resolidication at 2 K/
min and hence absence on second melting. The
absence of a smaller single peak at lower melting
onset temperature than the larger double peak in
the rst-cycle melting endotherm from the as-spun
Al0.3 wt% Fe0.1 wt% Si ribbon suggests that at
the even higher solidication rates experienced
during melt spinning, either FeAlm does not form,
or if it forms it then transforms during subsequent
reheating in the DSC prior to melting.
4402 ALLEN et al.: NUCLEATION OF SECONDARY PHASES
4.6. Summary of factors inuencing FeAlm formation
As discussed in Sections 4.5.1 and 4.5.2, neither
the presence of V nor grain rener are prerequisites
for the formation of FeAlm during solidication.
The importance of bulk Si content and solidica-
tion rate in the formation of FeAlm suggest that the
Si content of the interdendritic liquid during solidi-
cation is important in determining whether FeAlm
will form or not, assuming that liquid is free of
nucleants for Fe4Al13 which would otherwise work
at lower undercoolings. It appears that a minimum
concentration of Si must be exceeded for FeAlm to
form. EDX data from extracted particles [Fig. 2(b)]
does indeed indicate that FeAlm is richer in Si than
Fe4Al13. The Si concentration of the liquid can be
raised either by raising the bulk Si level or parti-
tioning a non-equilibrium amount of Si into the
liquid via a Scheil process during solidication. At
very high solidication rates, however, such as
those experienced during melt spinning, solute trap-
ping of the Si into the Al matrix will take place,
reducing the Si content of the interdendritic liquid
once more. Whether V, Zr [32] and grain rener ad-
ditions act to promote FeAlm by locally raising the
Si concentration in the liquid during partial melting
and resolidication is as yet unclear. More detailed
chemical analyses of the sites of FeAlm formation
are currently in progress [49].
5. CONCLUSIONS
The entrained droplet technique provides a suc-
cessful experimental means of studying the nuclea-
tion-controlled aspects of phase selection during the
nal stages of solidication in dilute alloys.
Impurity and grain rener additions inuence the
resolidication behaviour of melt-spun Al0.3 wt%
Fe0.1 wt% Si ribbons after partial melting. Both
high levels of V impurity (2500 ppm) or additions
of AlTiB grain rener promote the formation of
the metastable FeAlm phase at cooling rates as low
as 2 K/min. Lower levels of V (R100 ppm) act in
conjunction with AlB, AlTiB and AlTiC
grain rener additions to promote FeAlm formation.
Thus the level of V required to promote FeAlm
reduces from 2500 ppm in the absence of a grain
rener to <100 ppm in its presence.
The presence of FeAlm in commercial DC-cast
alloys [13] suggests that both V impurity and Al
TiB grain rener can play an important role in
phase selection during commercial casting processes,
in addition to the eects of solidication rate and
bulk Si content. Control of V and grain rener con-
tent in commercial alloys may therefore provide a
means of inuencing secondary phase content, and
ultimately material properties, without having to
redesign the alloy composition or change casting
parameters.
AcknowledgementsWe would like to thank the U.K.
Engineering and Physical Sciences Research Council and
Alcan International Ltd. for nancial support, and J.
Worth, A. Flemming and J. Brown of Alcan International
Ltd. for their guidance and assistance in the preparation
of alloys, in secondary phase extraction and EDX analysis,
and in WDX/EPMA analysis, respectively.
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