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THE EFFECT OF VANADIUM AND GRAIN REFINER ADDITIONS ON THE NUCLEATION OF SECONDARY PHASES IN 1XXX Al ALLOYS
THE EFFECT OF VANADIUM AND GRAIN REFINER ADDITIONS ON THE NUCLEATION OF SECONDARY PHASES IN 1XXX Al ALLOYS
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
Oxford, Parks Road, Oxford OX1 3PH, U.K. and 2Alcan International Limited, Banbury Laboratory,
Southam Road, Banbury, Oxfordshire OX16 7SP, U.K.
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
grain renement, was also investigated by studying from a commercial purity Al base containing
the solidication of Al droplets in a Zr aluminide 2500 ppm of impurities, originating from the
matrix [31]. smelting process, with a 1:1000 addition (by weight)
These techniques have been used recently to of Al3 wt% Ti1 wt% B grain rener alloy. All
study the impurity-catalysed nucleation of second- alloy compositions were determined by spark emis-
ary phases in 1xxx Al alloys [3234]. The purpose sion spectrographic analysis, in each case as the
of the present paper is to describe a detailed study mean of three analyses, and are listed in Table 1.
extending this work, concentrating on the eect of Samples of 25 g each of the high purity alloys and
V and grain rener additions. Melt spinning was the lower purity alloy were rapidly remelted in a
4
used to produce a dispersion of submicron second- quartz crucible under Ar at 4.5 10 Pa and melt-
ary phases in a higher melting point Al matrix, spun when at a temperature >8008C by ejection
which were then melted to form entrained eutectic through a 1 mm nozzle using an Ar overpressure of
4
liquid droplets in a solid Al matrix prior to cooling 1.5 10 Pa on to a Cu wheel rotating at 23 m/s.
and resolidication. As the droplets were dispersed, Two high purity alloys with combined additions of
each individual droplet required its own nucleant V and AlTiC grain rener were also melt-spun
for solidication, i.e. by dividing the liquid into when at other temperatures <8008C. All resulting
droplets the degree of nucleation control on second- ribbons were typically 0.11 m long, <5 mm wide
ary phase selection was greatly exaggerated over and 50150 mm thick.
that of growth. The resolidication of the droplets, Specimens of 22 mg from each ribbon were
and the eect of impurities on secondary phase sealed into either W- or Mo-lined Cu pans and ana-
nucleation was studied using DSC. Nucleation is lysed in either a TA Instruments 2010 DSC or a
one important factor that inuences secondary MettlerToledo 821e DSC, using an identically pre-
phase selection during the nal 1015% of solidi- pared W- or Mo-lined empty Cu pan as a reference.
cation during industrial casting processes also, Two cycles of partial melting and resolidication,
where a proportion of the remaining liquid becomes i.e. eutectic melting and resolidication of the sec-
pinched-o into puddles between the Al dendrite ondary phase particles only, were performed under
arms prior to solidication. a dynamic Ar atmosphere, by heating from 632 to
6588C at 2 K/min, resolidifying at 2 K/min to
2. EXPERIMENTAL 6328C, and then remelting and resolidifying once
more in an identical manner.
A series of high purity-based Al0.3 wt% Fe Solidication microstructures were investigated
0.1 wt% Si alloys consisting of >99.995 wt% pure by quenching DSC specimens from some of the rib-
Al, Fe and Si, with various additions of V, Si and bons in contact with a water-cooled steel block at
Al5 wt% Ti, Al5 wt%Ti1 wt% B, Al3 wt% dierent stages during resolidication after partial
Ti1 wt% B, Al2.2 wt% Ti1 wt% B, Al2.2 wt% melting. Specimens were quenched from: (i) the
B and Al5 wt% Ti0.02 wt% C grain reners highest temperature T experienced during partial
were manufactured by melting the components in a melting; (ii) an intermediate temperature I just after
resistance furnace then casting into steel moulds. the rst major resolidication peak; (iii) an end
The high purity alloys were compared with a lower temperature E immediately after all the major reso-
purity Al0.3 wt% Fe0.1 wt% Si alloy prepared lidication peaks; and (iv) 25008C, well below all
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
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
Ribbon T: end of partial melting I: between 1st E: after end of 25008C fully
and 2nd peaks major peak solid
the major resolidication peaks, i.e. when the pressure [3539], mounted on an amorphous C lm
microstructure was fully solid. The ribbons investi- and analysed using selected area diraction pattern
gated and the exact quench temperatures used in (SADP) analysis and electron microprobe analysis
each case are summarised in Table 2. (EPMA) using an energy dispersive X-ray (EDX)
Quenched specimens were mounted, ground, and LINK AN10000 detector on the JEOL 2000FX
then polished using colloidal silica. Specimens were TEM. The distribution of the chemical elements Al,
then examined in an ISI DS130 SEM operating at Fe, Si, V and Ti between the primary Al matrix
1020 kV. Quenched specimens were also ion and the secondary phase particles was examined
beam-thinned and examined in a JEOL 2000FX using both a wavelength dispersive X-ray (WDX)
TEM operating at 200 kV. To assist in secondary microprobe analyser on a JEOL 733 ``Superprobe''
phase identication, particles were extracted by dis- and an EDX detector on the ISI DS130 SEM.
solving the Al matrix in boiling butanol under Specimens analysed for Si content were polished
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. (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, let with a melting onset temperature in the range of
to avoid introducing contamination from the col- 649.7651.08C. Figure 1(b) shows typical rst-cycle
loidal Si polishing stage. resolidication DSC exotherms after partial melt-
ing, which all consisted of a large peak with a soli-
3. RESULTS dication onset temperature in the range of 652.0
653.18C, followed in the cases of the high purity
3.1. DSC ribbons by a smaller peak at a lower temperature.
Figure 1(a) shows typical rst-cycle partial melt- The exotherm from the lower purity ribbon con-
ing DSC endotherms, which all consisted of a doub- tained two smaller peaks at lower temperature,
denoted A and B. Table 3 lists rst- and second- smaller peaks on rst melting, although on remelt-
cycle melting and solidication onset and peak tem- ing following solidication at 2 K/min in the DSC
peratures from partial melting and resolidication these smaller peaks are again absent.
of all the melt-spun ribbons investigated, as listed The second-cycle resolidication DSC exotherms
in Table 1. Table 4 lists the onset temperatures of from all ribbons were all similar to the rst-cycle
all the smaller peaks observed at lower temperature resolidication exotherms as shown in Fig. 1(b),
on rst- and second-cycle solidication, denoted A and again consisted of a large peak with a solidi-
Q, which varied with ribbon composition in the cation onset temperature in the range of 652.4
range 640.7647.48C. 653.98C, followed in the case of the high purity rib-
Figure 1(c) shows typical second-cycle partial bons by a smaller peak at a lower temperature, the
melting DSC endotherms after partial melting and same as was observed on rst-cycle resolidication
resolidication, which all consisted of a large single after partial melting. The exotherm from the lower
peak with a melting onset temperature in the range purity ribbon contained two smaller peaks at lower
of 650.4651.48C, similar to the melting onset tem- temperature, again the same as were observed on
perature on rst-cycle melting, which was in the rst-cycle resolidication. The solidication onset
range of 649.7651.08C, and in the same position as temperatures of all these smaller peaks varied with
the doublet detected in the rst-cycle partial melting ribbon composition in the range of 640.0648.28C
endotherms. The endotherms from the lower purity as listed in Table 4.
ribbon, and from the high purity ribbon containing
either high V (560 ppm), grain rener (excluding 3.2. Microscopy
AlTiC), or low V (57151 ppm) plus grain rener 3.2.1. EDX analysis of extracted particles. Figures
also contained a smaller single peak at a melting 2(a) and (b) show EDX analyses from secondary
onset temperature 21.52 K lower, in the range phase particles extracted from the high purity base
648.7649.78C. Figure 1(c) shows this peak in the ribbon and the low V (125 ppm) plus Al5Ti1B
cases of the lower purity ribbon, labelled T, and the grain rener ribbon, respectively. Samples of both
high purity ribbons containing high V (560 ppm), ribbons were quenched from temperature E (refer
and low V plus AlTiB grain rener, labelled R to Table 2), i.e. after completion of all major solidi-
and S, respectively. The size of this smaller single cation peaks as detected by DSC. The ranges of Si
peak in the second-cycle partial melting DSC and Fe contents of the secondary phase particles
endotherms from the high purity ribbon containing extracted from the high purity base ribbon [Fig.
low V plus AlTiC grain rener increased with 2(a)], the high V (560 ppm) ribbon, the low V
decreasing melt-spinning temperature in the range (125 ppm) plus Al5Ti1B grain rener ribbon
7108008C, from virtually absent at 8008C to a [Fig. 2(b)] and the lower purity ribbon are summar-
similar size to that from the low V plus AlTiB ised in Table 5. In all analyses the only elements
grain rener at 27108C. detected were Al, Fe or Si. The ranges of Fe con-
Increasing the Si content of the high purity base tents of the particles extracted from all the ribbons
ribbon from 0.1 wt% to 0.2 wt% broadened the analysed were similar, in the range 1330 at.% Fe.
double melting peak observed in the rst-cycle melt- The ranges of Si contents from the high V ribbon,
ing endotherm and depressed its melting onset to from the low V plus Al5Ti1B grain rener ribbon
648.38C. These eects have been previously and from the lower purity ribbon were all similar,
explained to be due to the gradients of the ternary in the range 05 at.% Si. The range of Si contents
AlFeSi liquidus and solidus surfaces [34]. A smal- from particles extracted from the high purity base
ler single peak prior to the main melting peak was ribbon was higher, in the range 18 at.% Si.
also observed in the second-cycle melting 3.2.2. Particle identications by SADP analysis of
endotherm from the Al0.3 wt% Fe0.2 wt% Si extracted particles. In Figs 2(a) and (b) solid circles
ribbon, which had only been present in the corre- indicate particles that were suciently thin to be
sponding endotherm from the Al0.3 wt% Fe identied by SADP analysis.
0.1 wt% Si ribbon on the addition of sucient V or 3.2.2.1. High purity base ribbon. Particle B1 [Fig.
grain rener [see Fig. 1(c)]. 2(a)] was identied by SADP analysis to be the
A similar double melting peak was also observed equilibrium Fe aluminide Fe4Al13 [40]. Figure 3
in the rst-cycle melting endotherms from the high shows a bright eld TEM micrograph of particle B2
purity Al0.3 wt% Fe0.1 wt% Si alloy in the as- [Fig. 2(a)]. Particle B2 could not be identied from
mould-cast condition, with two additional smaller SADP analysis as any known Fe aluminide (e.g.
peaks at lower temperature. These smaller peaks Fe4Al13, FeAl6 or FeAlm) or more Si-rich phase
were absent in the second melting endotherm, and (e.g. a-AlFeSi, b-AlFeSi or Si). This indicates that
the double peak had become a single peak, in a more than one type of phase is present in the high
manner analogous to that seen in the endotherms purity base ribbon when quenched from tempera-
from the melt-spun ribbons [cf. Figs 1(a) and (c)]. ture E.
In other words, decreasing the solidication rate 3.2.2.2. High V ribbon. Figures 4(a) and (b) show
(from melt spinning to mould casting) introduces 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. 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) rich secondary phases on the cell boundaries and
shows a typical backscattered electron image (BEI) within the cells, and a precipitate-free zone either
of the high purity base ribbon quenched from the side of the cell boundaries. Figures 6(b) and (c)
highest temperature T (Table 2) before any second- show higher magnication secondary electron
ary phase resolidication took place. The micro- images (SEIs), indicating the ne-scale eutectic
structure consisted of equiaxed Al cells, with Fe- microstructure of the secondary phases both at the
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 bon, the low V plus Al5Ti1B grain rener ribbon,
that all secondary phases solidied rapidly, i.e. that and the lower purity ribbon. Figure 8 shows a
they were liquid prior to the point of quench. TEM micrograph of an in situ intracellular phase
When the high purity base ribbon was quenched from the lower purity ribbon quenched from tem-
from temperature E [Table 2], after the major reso- perature I (Table 2), i.e. after the major resolidica-
lidication peak [as shown in Fig. 2(a)], the cell tion peak, but before peaks A and B [Fig. 1(b)].
boundary phases were blockier and more faceted Figure 8 shows the ne structure present in the in-
than when quenched from temperature T, before tracellular phase, indicating that it was an isolated
the major resolidication peak. This indicated that droplet of liquid prior to the point of quench.
the cell boundary phases solidied during the major The intracellular phases in the high V ribbon, the
resolidication peak. The intracellular phases low V plus Al5Ti1B grain rener ribbon, and the
retained the ne-scale eutectic structure indicating lower purity ribbon quenched from temperature E,
they were still liquid after the end of the major i.e. below the end of peaks G, P and B, respectively
resolidication peak. [Fig. 1(b)], were blockier and more faceted than
Figure 7 shows a typical BEI of the intracellular when quenched from temperature I, above the
phases in the high purity base ribbon quenched onset of peaks G, P and A, respectively. The par-
from a temperature of 25008C, well below the ticle morphologies were more similar to those seen
major resolidication peak observed by DSC. The in the high purity base ribbon when quenched from
intracellular secondary phases were blockier and 25008C (Fig. 7). Peaks G, P, A and B therefore
more faceted than when quenched from tempera- correspond to the solidication of the intracellular
ture E, just after the major resolidication peak. secondary phases.
This indicated that in the high purity base ribbon 3.2.4. Distribution of elements in the solidication
the intracellular phases undercooled and resolidied microstructures. Both WDX/EPMA and EDX ana-
at temperatures below the end of the major resolidi- lyses of SEM bulk specimens, and EDX analyses of
cation peak. This resolidication is just detected TEM foils, indicated that none of these techniques
by DSC as the broad, indistinct exotherm labelled were able to detect readily either V in the ribbons
C in Fig. 1(b). containing R125 ppm V, or Ti in ribbons containing
The correspondence of the major resolidication grain rening additions of R1:1000 addition level.
peak to the solidication of secondary phases at the Figures 9(a) (d) show the EPMA Fe, Si, Ti and
cell boundaries was also observed in the high V rib- 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
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]. 4.2. Intracellular liquid droplet solidication and
Comparison of microstructures quenched from remelting in the absence of impurities
before and after the Fe4Al13 resolidication peak The resolidication behaviour of the intracellular
shows that Fe4Al13 solidication occurs predomi- liquid droplets depends upon the trace chemistry of
nantly on the Al cell boundaries. Remelting of the the ribbon. In the high purity base ribbon the liquid
Fe4Al13 is detected as the large single peak common droplets undercool to temperatures below the end
to all second-cycle melting endotherms [Fig. 1(c)]. 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 has been previously attributed to be due to the pre-
detected by DSC as the broad, indistinct exotherm, sence of trace levels (23 ppm) of phosphorus [32].
labelled C in Fig. 1(b). Only Fe4Al13 is detected on The phase to which this peak corresponds remains
remelting, however, as shown in Fig. 1(c), indicating to be identied, however.
that the liquid droplets solidify at 2 K/min either as Comparison of microstructures quenched from
Fe4Al13 or as a metastable phase which rapidly before and after the FeAlm resolidication peak
transforms to Fe4Al13 on reheating prior to remelt- shows that FeAlm solidication occurs predomi-
ing. EDX data from particles extracted following nantly within the Al cells. Remelting of the FeAlm
quenching (at 2300 K/min), Fig. 2(a) indicate that is detected, prior to the remelting of the Fe4Al13, as
phases with a higher Si content than Fe4Al13 can a small single peak labelled R, S and T in the sec-
indeed form. The morphology of one such phase as ond-cycle melting endotherms from the high V rib-
observed by TEM [Fig. 6(a)] suggests that these bon, the low V plus Al5Ti1B grain rener ribbon
higher Si content phases form within entrained and the lower purity ribbon, respectively, as shown
liquid droplets that can reach higher undercoolings in Fig. 1(c), with a melting onset temperature in the
than the liquid at the cell boundaries. These phases, range of 648.7649.78C. The metastability of the
however, rapidly transform to Fe4Al13 on reheating FeAlm phase has been previously conrmed by iso-
and consequently only Fe4Al13 is detected on thermal holding in the solid state prior to remelting
remelting. [34], which reduces the area of the subsequent
FeAlm melting peak.
4.3. Intracellular liquid droplet solidication and The FeAlm remelting peak is also detected in the
remelting in the presence of impurities second-cycle melting endotherms from the ribbons
4.3.1. FeAlm solidication and remelting in containing grain rener (excluding AlTiC), and
entrained liquid droplets. On the basis of mor- low V (57151 ppm) plus grain rener. The smaller
phology, Fe4Al13 and FeAlm cannot be readily dis- peaks present in the resolidication exotherms from
tinguished in dilute Al alloys. On the basis of these ribbons therefore also correspond to the reso-
SADP analysis, the EDX data from particles lidication of the FeAlm phase, the solidication
extracted from the high V ribbon, the low V plus onset temperature varying with the trace chemistry
Al5Ti1B grain rener ribbon, and the lower of the ribbon in each case.
purity ribbon can be divided into two groups: Si 4.3.2. Formation of other phases on solidication
contentR22.7 at.% Si and > 22.7 at.% Si, corre- and remelting of entrained liquid droplets. FeAlm is
sponding to Fe4Al13 and FeAlm particles, respect- not formed in the low V (R125 ppm), and AlTiC
ively. The mean composition of group I is 22.0 at.% grain rener ribbon. The smaller peaks present in
Fe, 1.3 at.% Si (quoted to the nearest 0.5 at.% Fe the resolidication exotherms from these ribbons
and 0.1 at.% Si), which correlates well with the therefore correspond either to the solidication of
value of 22.5 at.% Fe, 1.5 at.% Si calculated from undercooled Fe4Al13 or of a metastable phase
published values for Fe4Al13 in DC-cast alloys of which rapidly transforms to Fe4Al13 on reheating
similar bulk Si content [2, 4244]. Stacking faults prior to remelting as was the case for the high
on {001} and associated spot streaking along {001} purity base ribbon (Section 4.2). One such phase
in reciprocal space from the SADPs of particles in may be the other common metastable AlFe eutec-
group I [Fig. 4(a)] are also characteristic of Fe4Al13 tic, FeAl6. A number of workers [45] have noted
[40]. The mean composition of group II is 19.5 at.% that FeAl6 rapidly transforms to Fe4Al13 at tem-
Fe, 3.4 at.% Si, which correlates well with the value peratures just below the eutectic temperature, and
of 18.0 at.% Fe, 3.1 at.% Si calculated from pub- that the presence of Si accelerates this transform-
lished values for FeAlm in DC-cast alloys of similar ation.
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 4.4. FeAlm formation
[41]. 4.4.1. Combined action of V plus AlTiB grain
FeAlm forms as a minority phase on resolidica- rener in lower purity ribbon. The occurrence of
tion at 2 K/min after partial melting of the high V FeAlm during DC casting of commercial purity
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- ribbon 2100 ppm V promotes the formation of
dication corresponds to the smaller single peaks FeAlm. However, in high purity ribbon 2500 ppm
G, P and A, respectively, in Fig. 1(b), with a solidi- V is necessary [32]. The addition of AlTiB grain
cation onset temperature in the range of 644.9 rener to this ribbon promotes FeAlm formation at
647.38C. This peak follows the large resolidication V levels of 2100 ppm. The presence of AlTiB
peak of Fe4Al13 common to all resolidication exo- grain rener in the lower purity ribbon therefore
therms [Fig. 1(b)]. The peak labelled B in the resoli- acts in conjunction with the V present to promote
dication exotherms from the lower purity ribbon FeAlm formation.
ALLEN et al.: NUCLEATION OF SECONDARY PHASES 4401
4.4.2. Combined action of V plus AlTiC grain cal analyses of quenched liquid droplets. No Ti was
rener and eect of melt-spinning temperature. The detected in the Fe aluminides in AlTiB grain re-
size of the peak attributed to the melting of FeAlm ner containing alloys [cf. Figs 9(a) and (c)]. AlTi
observed in the second-cycle melting endotherm B grain reners have been shown to contain two
when Al5Ti1B grain rener is added to the low V types of Ti-rich particles, TiAl3 and TiB2 [48]. The
ribbon is much larger than when AlTiC grain small Ti-containing particles shown in Fig. 9(d) are
rener is added. Under identical melt-spinning con- thought to be TiB2 particles that originate from the
ditions, therefore, less FeAlm forms in ribbons con- grain rener addition, as TiAl3 particles are known
taining V plus AlTiC than V plus AlTiB. The to become unstable and dissolve when added to di-
amount of FeAlm that forms in the V plus AlTiC lute Al alloys [48]. Thus TiB2 particles do not
grain rener alloy increases, however, as melt-spin- appear to be associated with the Fe aluminides in
ning temperature decreases, as reported in Section the microstructure, contrary to the proposals of
3.1. The sensitivity of FeAlm formation to the melt previous workers [4, 5052]. WDX analysis shows
superheat experienced during processing is similar that V is partitioned into the Al matrix [Fig. 9(d)],
to the sensitivity of primary grain renement by away from the Fe aluminides during partial melt-
AlTiC [46,47] to casting temperature, suggesting ing, as would be expected from the peritectic nature
that the amount of FeAlm formed may be linked to of the AlV binary phase diagram. However, given
the as-solidied primary grain size. However, other the slow diusion of V in solid Al, this may provide
results discussed below (Section 4.4.3) indicate that a mechanism for concentrating V in a shell sur-
primary grain renement does not play a role in the rounding the entrained liquid puddle. The width of
promotion of FeAlm. this shell would probably be too narrow to be
4.4.3. Eect of Ti:B ratio in AlTiB grain re- detected by EPMA techniques applied to bulk spe-
ner. The size of the peak attributed to the melting cimens.
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 4.5. Role of interdendritic liquid composition
2.2Ti1B grain rener is added, i.e. the amount of 4.5.1. Importance of bulk Si content. The presence
FeAlm formed does not change signicantly with of a smaller single peak at a lower melting onset
Ti:B ratio. For eective primary grain renement temperature than the larger single peak in the sec-
by AlTiB addition, however, a stoichiometric ond-cycle melting endotherm from the high Si Al
excess of Ti is necessary [48]. The insensitivity of 0.3 wt% Fe0.2 wt% Si ribbon, as reported in Sec-
FeAlm formation to Ti:B ratio therefore suggests tion 3.1, indicates that increasing the Si level from
that the amount of FeAlm formed is not linked to 0.1 wt% to 0.2 wt% promotes the formation of
the as-solidied primary grain size. FeAlm during resolidication after partial melting.
4.4.4. Grain size in partially melted and resolidied This indicates that in alloys of a suciently high Si
ribbons. Comparison of grain sizes in microstruc- content neither V nor grain rener is a prerequisite
tures quenched prior to FeAlm formation following for FeAlm formation.
partial melting and resolidication indicates that 4.5.2. Importance of solidication rate. The pre-
any grain size dierences that exist with ribbon sence of two smaller single peaks at lower melting
composition prior to partial melting are removed onset temperatures than the larger double peak in
by grain coarsening in the partially molten state the rst-cycle melting endotherm from the as-
[49]. This also indicates that the amount of FeAlm mould-cast Al0.3 wt% Fe0.1 wt% Si alloy, as
formed is not linked to the as-melt-spun primary reported in Section 3.1, indicates that metastable
grain size. phases (i.e. including FeAlm) form during mould
4.4.5. Role of direct nucleation by grain rener casting, even in the absence of V and grain rener,
particles. The size of the peak attributed to the soli- and do not subsequently fully transform to Fe4Al13
dication of FeAlm observed in the rst-cycle resoli- during heating in the DSC. These metastable phases
dication exotherm when Al5Ti1B grain rener is form due to the higher solidication rate experi-
added to the low V ribbon is similar to that when enced during mould casting compared to during
AlB grain rener is added. The promotion of controlled cooling at 2 K/min in the DSC, explain-
FeAlm by AlB, AlTiB (Section 4.4.1) and Al ing their removal following resolidication at 2 K/
TiC additions (Section 4.4.2) shows that the min and hence absence on second melting. The
chemical identity of the grain rener in the pro- absence of a smaller single peak at lower melting
motion of FeAlm is unimportant. This suggests that onset temperature than the larger double peak in
FeAlm is not directly nucleated either by the corre- the rst-cycle melting endotherm from the as-spun
sponding grain rener particles (AlB2, TiB2 or TiC, Al0.3 wt% Fe0.1 wt% Si ribbon suggests that at
respectively) or some reaction product between V the even higher solidication rates experienced
and the grain rener particles. Further evidence during melt spinning, either FeAlm does not form,
that FeAlm is not directly nucleated by the grain or if it forms it then transforms during subsequent
rener particles is provided by the results of chemi- reheating in the DSC prior to melting.
4402 ALLEN et al.: NUCLEATION OF SECONDARY PHASES
4.6. Summary of factors inuencing FeAlm formation AcknowledgementsWe would like to thank the U.K.
Engineering and Physical Sciences Research Council and
As discussed in Sections 4.5.1 and 4.5.2, neither Alcan International Ltd. for nancial support, and J.
the presence of V nor grain rener are prerequisites Worth, A. Flemming and J. Brown of Alcan International
for the formation of FeAlm during solidication. Ltd. for their guidance and assistance in the preparation
of alloys, in secondary phase extraction and EDX analysis,
The importance of bulk Si content and solidica- and in WDX/EPMA analysis, respectively.
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
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