Materials Science and Engineering A354 (2003) 188
/198

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Examination of the effect of Sc on 2000 and 7000 series aluminium

alloy castings: for improvements in fusion welding
A.F. Norman a,*, K. Hyde a, F. Costello a, S. Thompson b, S. Birley b, P.B. Prangnell a
a
Manchester Materials Science Centre, University of Manchester and UMIST, Grosvenor Street, Manchester M1 7HS, UK
b
QinetiQ, Future Systems Division, Ively Rd, Farnborough, Hampshire GU14 0LX, UK

Received 2 September 2002; received in revised form 9 December 2002

Abstract

It has been reported that small additions of scandium (Sc) can improve the weldability and mechanical properties of some
aluminium aerospace alloys that are normally considered to be unweldable. In order to determine the mechanisms by which these
improvements occur, and more rapidly arrive at optimum Sc addition levels, small wedge-shaped castings have been used to
simulate the cooling rates found in MIG/TIG welds. Using this technique, a range of Sc addition levels have been made to two
typical Al-aerospace alloys, 2024 and 7475. It has been found that when the Sc level exceeds a critical concentration, small Al3Sc
primary particles form in the melt and act as very efficient grain nucleants, resulting in simulated fusion zone grain sizes as fine as 15
mm. This exceptional level of grain refinement produced an unusual grain structure that exhibited no dendritic, or cellular,
substructure and a large increase in strength and ductility of the castings. Sc also produced changes in the alloys freezing paths,
which cannot yet be fully explained, but led to the appearance of the W phase in the 2024 alloy and, in both alloys, an overall
reduction in the amount of eutectic formed during solidification. When coupled with the high level of grain refinement, this
behaviour could be used to explain the increased strength and ductility of the castings. In 2000 and 7000 series aluminium alloys, it is
therefore, anticipated that optimised Sc bearing filler wires will significantly improve the mechanical properties of the weld metal, as
well as reducing the tendency for solidification cracking.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Aluminium aerospace alloys; Scandium; Grain refinement; Solidification behaviour; Welding

1. Introduction are severest in aerospace alloys, like the Mg containing

In recent years, the welding of aluminium aerospace-
alloys has received renewed attention, because of the
need to reduce the high manufacturing costs associated
with the fabrication of riveted, or fastened, airframe
structures. However, many of the Al-alloys that are
currently used in aircraft are considered to be not
recommended for fusion welding [1,2]. Particular pro-
blems that limit their weldability, include: solidification
cracking within the fusion zone, liquation cracking at
the boundary between the fusion zone and the HAZ,
and poor corrosion performance [1
/3]. These problems
* Corresponding author. Present address: Corus RD & T, Swinden
Technology Centre, Moorgate, Rotherham S60 3AR, UK. Tel.: /44-
1709-82-5318; fax: /44-1709-82-5337.
E-mail address: andrew.norman@corusgroup.com (A.F. Norman).
2000 series (e.g. 2014 and 2024), and Cu containing 7000
series alloys (e.g. 7475, 7150), as these materials tend to
have a wide freezing range and form low melting point
eutectic phases.
Solidification cracking occurs when the thermal
stresses that build up during freezing exceed the strength
of the solidifying weld metal [2,4]. Methods that are
commonly used to reduce the tendency for solidification
cracking include: altering the weld composition, through
the addition of a filler wire, close process control, and
controlling the grain structure within the fusion zone
[1,2]. For example, it is widely accepted that by changing
the welds grain structure, from coarse columnar to fine
equiaxed, a better cohesion strength can be obtained,
and the remaining eutectic liquid present during the final
stages of solidification can feed more easily, and heal
any cracks that may form [2,4].

0921-5093/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0921-5093(02)00942-5
 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
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Another important drawback to fusion welding 2000
and 7000 series alloys is their poor fusion zone strength
and ductility. This is a particular problem for compo-
nents containing unreinforced welds, and in aerospace
structures, good strength levels are required to obtain a
high joint efficiency. Unfortunately, commercially avail-
able Al-filler wires have not been specifically developed
for aerospace alloys and currently provide insufficient
strength for many applications. In some cases the joint
strength levels can be as low as 50% of the parent
properties [5]. Furthermore, they do not alleviate the
problems of solidification cracking in alloys such as
2024, and Cu bearing 7000 series alloys, like 7475 and
7050.
The alloy addition Sc has recently become of con-
siderable interest to the aluminium welding community,
as it has been claimed that small concentrations of Sc
can produce enhanced weldability in Al-alloys that are
susceptible to solidification cracking and can also
improve their weld metal strengths [6]. The original
research on Sc additions to aluminium was carried out
in the former Soviet Union (e.g. [7
/9]). More detailed
studies of the solidification behaviour of Al
/Sc alloys
have now been published in the West and confirm many
of the earlier observations made by Russian scientists
(e.g. [10
/12]). However, to date, this information has
mainly been limited to simple alloy systems. Further-
more, the limited published work that has claimed
substantial improvements in the properties of Sc con-
taining fusion welds, has not provided optimised
compositions or investigated in detail the underlying
mechanisms as to why such improvements are found
(e.g. [6
/9,13]).
The long-term aim of the current research programme
at Manchester is to develop a new generation of Sc
containing filler wires that will improve the weldability
of 2000 and 7000 series Al aerospace alloys. However,
the manufacture of filler wires is a time consuming and
expensive process. Therefore, to minimise the number of
experimental wire compositions that are required, small
wedge shaped castings have been used as a method of
simulating the cooling rates, typically found in the
fusion zones of MIG and TIG welding processes. By
using this approach, and adding a range of Sc levels to
the alloys of interest, potential optimum filler composi-
tions can be rapidly identified that can subsequently be
made into wire and tested (the results of the welding
trials obtained with the filler wire compositions identi-
fied from this investigation will be the subject of another
publication [14]). The two parent alloys selected for
investigation were based on (i) AA2024 and (ii) AA7475,
which are typical examples of commonly used 2000 and
7000 series aerospace alloys. Metallography was used to
investigate the ability of Sc to refine the fusion zone
grain structures, whereas DSC and XRD were used to
study the effect of Sc on the phase formation and
189
freezing paths of the alloys. This second aspect of the
work is important, as little is currently known about
how Sc interacts with multi-component commercial Al-
alloys. To gain an insight into the performance of the Sc
modified solidification structures, and to assess the
effect of Sc on potential weld fusion zone properties,
the tensile behaviour of the castings was studied as a
function of the Sc content and cooling rate. Relation-
ships between the freezing behaviours and properties of
the Sc containing alloys are then discussed.
2. Experimental
The different alloy compositions used in this study
were prepared using master alloys and commercial
purity Al (99.7%). The Sc-free baseline alloys had
nominal compositions approximately equivalent to,
AA2024 and AA7475, of Al
/4.5%Cu
/1.5%Mg and
Al
/5.5%Zn
/2.2%Mg
/1.5%Cu, respectively. These al-
loys are referred to as 2024 and 7475 below. Sc
additions were made to the melts using an Al
/2%Sc
master alloy, to give concentrations from 0 to 0.8 wt.%
Sc. Sc was added either on its own, or in conjunction
with 0.12% Ti and 0.15% Zr (see below for details). The
different alloy compositions were cast into a wedge-
shaped mould, that produced cooling rates from 10 K
s 1, at the top of the mould, to 100 K s 1 near the
wedge tip. The cooling rate at the wedge tip was,
therefore, similar to that found in TIG and MIG weld
pools [10]. After casting, each alloy was analysed using
wet chemical analysis to verify that the actual composi-
tions fell close to the nominal compositions, specified
above. It should be noted that the Sc-free baseline
castings did not contain Ti/TiB2. All the compositions
given here and below are quoted as weight percentages.
After casting, sections were taken from three positions
along the centreline of each wedge casting, which
corresponded to different cooling rates (the top, centre
and tip). To reveal the grain structure for optical
metallography, the samples were anodised in Barkers
reagent and examined under polarised light. For SEM
examination, samples were lightly electropolished and
subsequently examined in a Philips FEGSEM, operated
at 10 kV. Cylindrical tensile specimens were machined
from the same three locations in the castings, with a
gauge diameter of 6 mm and a gauge length of 50 mm,
and tested at an applied strain rate of
/103 s 1, 1
month after casting. Grain size measurements were
made using the mean linear intercept method [15].
DSC measurements were made using a Netzsch 204
and a Perkin
/Elmer Pyris 1 DSC. For each composition
studied, between 20 and 80 mg of material was melted in
the DSC pan and cooled from above the liquidus
temperature, at a rate of 10 8C min 1 in an argon
atmosphere.
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3. Results and discussion
3.1. The solidification behaviour of binary Al
/Sc alloys
Before considering the interaction of Sc with the more
complex alloys of prime interest, it is useful to first
summarise results that have previously been reported for
the solidification behaviour of the simpler binary Al
/Sc
system [10]. The Al-rich end of the Al
/Sc equilibrium
phase diagram, shown in Fig. 1a [16], is dominated by a
eutectic reaction between L, a and Al3Sc. The equili-
brium Al3Sc phase has an ordered L12 cubic crystal
structure, and the eutectic point occurs at 0.55% Sc and
655 8C, which is only 10 8C below the melting point of
Fig. 1. (a) The Al-rich end of the Al
/Sc equilibrium phase diagram
[16]. Examples of typical cast microstructures for a hypoeutectic Al
/
0.2% Sc alloy, showing a large columnar dendritic grain structure, and
a hyper eutectic Al
/0.7% Sc alloy, showing highly refined equiaxed
grains with no sub-structure, are given in (b) and (c), respectively.
Al. For hypoeutectic compositions (containing less than
0.55% Sc), on cooling from the liquid, the first phase to
form is a-Al and, and when no external grain refiners
are used, the grain structure on solidification is coarse,
as might be expected in most conventional alloys (Fig.
1b). However, when the Sc level exceeds the eutectic
point, on crossing the liquidus the L12 Al3Sc phase
precipitates first from the melt, as small cubic primary
particles [11]. Due to the close similarity between the L12
crystal structure and the FCC a-Al matrix, and the small
lattice mismatch (
/1.5%), the Al-3Sc particles act as
excellent nucleation sites for a-Al grains [9,10], resulting
in a very high level of grain refinement (Fig. 1c). In a
binary alloy, grain refinement, therefore, only occurs
once a critical Sc level is exceed that corresponds to the
a-Al/Al3Sc eutectic point. Unusually, the refined
grains have been observed to contain no cellular or
dendritic substructure [10]. This has previously been
explained in terms of the high nucleation efficiency of
the Al3Sc phase, as grains nucleating at a low under-
cooling on a high density of nucleation sites will impinge
before their initially spherical growth front becomes
morphologically unstable [10].
3.2. Grain structures of the 2024 and 70475 castings
3.2.1. The 2024 alloy
The typical grain structure seen at the centre of the
wedge casting with the Sc (and grain refiner) free 2024
alloy, is shown in Fig. 2a, and unsurprisingly consists of
large columnar grains with a dendritic substructure. The
grain size at the tip of the casting was
/250 mm, and
this increased to
/1 mm near the top surface. For
dilute additions of 0.2 and 0.4% Sc, shown in Fig. 2b
and c, there was little change in the grain structure
throughout the casting, although there was a slight
reduction in grain size. However, when Sc additions of
0.6%, or above, were made to the base alloy, a dramatic
refinement in the grain size was observed throughout the
casting, as can be seen in Fig. 2d. This behaviour is very
similar to that seen in the binary system (see above
Section 3.1). The refined grain size was reduced to
/40
mm, and
/150 mm near the tip and top of the wedge
casting, respectively, which is an order of magnitude
smaller than in the base alloy. Moreover, for the grain-
refined castings, no sub-structure was visible within the
fine equiaxed grains, suggesting, as discussed above
(Section 3.1), that the grains impinged before their
growth front became unstable (Fig. 2f). This same
behaviour has also been reported in a ternary Al
/Cu
/
Sc alloy with a similar Sc level by the present authors
[10]. For compositions of 0.6% Sc and above, L12 Al3Sc
primary particles could be seen at the centre of some
grains, indicating that the grain refining mechanism is
similar to that found in the binary system. However,
primary Al3Sc particles were also commonly observed at
 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
/198 191

Fig. 2. Optical micrographs taken from the centre of the 2024 Al-alloy castings, showing in; (a) the base alloy with no Sc, (b) 2024/0.2% Sc, (c)
2024/0.4% Sc, (d) 2024/0.6% Sc, and (e) the 2024 alloy with 0.4% Sc, plus 0.12Zr/0.15Ti, In (f) a higher magnification image of (d) shows the lack
of substructure and the presence of Al3Sc primary particles in the refined alloys.

the grain boundaries were they had been pushed during
freezing and had presumably not taken part in the
nucleation process (for example see Fig. 2f).
Prior work on Al
/Sc alloys [17] has demonstrated
that adding both Zr and Ti in conjunction with Sc can
reduce the amount of Sc required to achieve grain
refinement, as well as the overall grain size. This is
thought to occur because Zr and Ti can substitute for Sc
in the Al3Sc phase, and is obviously advantageous
because of the relatively high cost of Sc. To verify
whether this effect would also take place in a 2000 series
alloy, further castings were made that included additions
of 0.12Zr and 0.15Ti (these levels were chosen because
they are the maximum that can normally be used in a Sc-
free Al-alloy without forming primary particles). When
Zr and Ti were added to the base alloy, the minimum
amount of Sc required to produce grain refinement was
indeed reduced, to 0.4% Sc, as can be seen in Fig. 2e.
However, the refined grain size was still very similar to
that seen when 0.6% Sc was used without Ti and Zr (Fig.
2d).
3.2.2. The 7475 alloy
The microstructure of the Sc-free 7475 alloy casting
was very similar to that seen with the Sc-free 2024
control alloy, and was again comprised of very large
grains with a dendritic substructure (Fig. 3a). Since the
beneficial effects of using combined additions of Sc with
Zr and Ti, found with the 2024 alloy, in the case of the
7475 alloy, Sc additions were always made in conjunc-
tion with the same fixed level of 0.12% Zr and 0.15% Ti.
However, in this case, grain refinement was observed
when a concentration of as little as 0.2% Sc was reached
in the castings, (Fig. 3b) as opposed to the higher
concentration of 0.4% required for the 2024 alloy (when
Ti and Zr were present). Furthermore, even with this
lower Sc level, the refined grain size was considerably
192 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
/198

Fig. 3. Optical micrographs taken from the centre of the 7475 Al-alloy castings, showing in; (a) the base alloy with no Sc, (b) 7475/0.2% Sc, (c)
7475/0.4% Sc, (d) 7475/0.6% Sc, and (e) the base alloy/0.8% Sc. In all cases Sc additions were made in conjunction with 0.12% Zr and 0.15% Ti.

smaller than seen in the 2024 alloy, being 25 as opposed
to 40 mm at the tip of the castings (Fig. 2e, Fig. 3b).
When greater additions of Sc, than the minimum
required for refinement, were made to the 7475 casting
the grain size continued to slowly reduce. For example,
at the mould tip the grain size decreased from
/25 mm,
with 0.2% Sc (Fig. 3c), to as small as
/15 mm for a 0.8%
Sc concentration (Fig. 3e). It should be emphasised at
this stage that these are extremely fine grain sizes for
aluminium castings, that cannot normally be achieved
using conventional grain refiners such as Ti/TiB2.
3.3. Tensile properties of the castings
3.3.1. The 2024 alloy
Tensile tests were performed on specimens machined
from the tip, centre, and close to the top surface of the
wedge-shaped castings, giving data for a range of
cooling rates. The resultant tensile properties measured
are given in Table 1 and, for the 2024 alloys, show that
when the Sc level was too low to exhibit a refined grain
structure (B/0.6% Sc) tensile strengths of 170
/200 MPa
were typical. These compositions also exhibited almost
zero ductility, as might be expected from castings having
a very large grain size and containing grain boundary
eutectic phases (see below, Section 3.4). In sharp
contrast, those alloys which contained sufficient addi-
tions of Sc to refine the grain size produced an increase
in strength of
/100 to around 300 MPa. More
significantly, these alloys showed reasonable ductilities,
for an as-cast 2024 structure, of 3
/5%. This is higher
than the level of ductility that is usually observed in
conventional Sc-free MIG or TIG welds with a similar
alloy composition [5].
3.3.2. The 7475 alloy
The unrefined 7475 Sc-free casting also had poor
mechanical properties (Table 1), with a tensile strength
of
/200 MPa and almost zero ductility. When an
 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
/198 193

Table 1
Tensile properties of the 2024 and 7475 alloy castings

Tip of casting Centre of casting Top of casting

UTS (MPa) % El. UTS (MPa) % El. UTS (MPa) % El.

2024 Base 187 0 185 0.5 145 0

2024/0.2Sc 184 0 188 0 88 0
2024/0.6Sc 216 1 212 0.5 147 0
2024/0.8Sc 273 3 293 3 246 1.5
2024/4Sc* 304 3.5 291 1.5 230 1.5
7475 Base* 183 0 215 0 206 0
7475/0.2Sc* 290 0.5 307 0.5 294 0.5
7475/0.4Sc* 371 4 345 2 310 1.5
7475/0.6Sc* 382 3 384 1.5 298 1.5
7475/0.8Sc* 355 1.5 370 2 307 1

The compositions marked * contain 0.12% Zr and 0.15% Ti.

addition of 0.2% Sc was made (together with 0.12% Zr
and 0.15% Ti), the strength increased to
/ 300 MPa,
although, at 0.5%, the ductility of this casting was only
slightly better than the base alloys. This poor elonga-
tion occurred despite the fact that there was sufficient Sc
in the alloy to produce a greatly refined grain structure
(see Fig. 3b). However, when the Sc level was increased
to 0.4%, the ductility of the casting increased substan-
tially and the strength also rose further, giving an
elongation of 4% and a tensile strength of 380 MPa at
the wedge tip. Although there is some scatter in the data,
it was noticeable that at higher addition levels than 0.4%
Sc there was a trend for the castings ductilities to
decline (this is most apparent at the wedge tip in Table
1).
3.4. Phase formation during solidification
To fully explain the relationships between the im-
provement in tensile properties and the Sc concentration
in the different castings (which did not necessarily
coincide exactly with the minimum Sc level required
for grain refinement), DSC, XRD and SEM analysis
were performed on samples taken from the centre of
each casting. The main aim of this study was to
determine whether Sc had affected the solidification
behaviour of the alloys, other than by the formation of
primary Al3Sc particles and the associated grain refine-
ment reported above (Section 3.2).
Al2Cu and S-Al2CuMg (see Fig. 4). A DSC trace taken
from the 2024 alloy is shown in Fig. 5 and contains two
peaks, one at
/550 8C and the other at
/500 8C,
apart from the main solidification exotherm at 640 8C
(L 0/L/a-Al) which is not shown on the trace. The
liquidus plan for the ternary Al
/Cu
/Mg alloy system,
calculated using MTDATA and the COST507 light alloys
data base [18], is depicted in Fig. 6a. According to this
diagram, for an alloy with the same Cu and Mg content
as 2024 (4.5% Cu, 1.5% Mg), on freezing the first phase
to form from the liquid is a-Al and this gives rise to the
main solidification peak seen on crossing the liquidus at

/640 8C. As solidification proceeds, solute is rejected
and the liquid Cu and Mg concentration increases, until
the univariant line (U1 in Fig. 6a) is reached. This point
is coincident with the 550 8C peak on the DSC trace
(Fig. 5). Below this temperature, a-Al and u-Al2Cu
solidify simultaneously as a eutectic, and the liquid
composition subsequently follows the univariant line
until the ternary eutectic reaction is reached, at E1 (see
Fig. 6a). The final liquid then solidifies isothermally, via
this ternary eutectic reaction, to form a-Al, u-Al2Cu,
and S-Al2CuMg, amd corresponds to the lowest tem-
perature peak seen on the DSC trace at
/505 8C (Fig.

3.4.1. The 2024 alloy

In the Sc-free 2024 base alloy, the XRD and DSC
results were found to be entirely consistent with the
known solidification behaviour of AA2024 [1]. The DSC
and XRD results discussed below, in the context of the
effect of increasing Sc concentration on the solidifica-
tion path of 2024, can therefore, be considered reliable. Fig. 4. X-ray diffraction traces, for the 2024 Sc-free base alloy,
As expected [1], XRD analysis of the 2024 base alloy showing the presence of the u and S phases, and the 2024 alloy with
revealed the presence of three main phases, a-Al, u- an addition of 0.8% Sc, showing the presence of the u, S and W phases.
194 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
/198
Fig. 5. DSC traces showing the 2024 base alloy, and 2024 plus Sc
levels of 0.2, 0.4, 0.6 and 0.8% Sc.
Fig. 6. Liquidus plans for, (a) the Al
/Cu
/Mg alloy system, calculated
using MTDATA [18], and (b) the Al-rich corner of the Al
/Cu
/Sc alloy
system (adapted from [9]).
5). The overall melting range of the base alloy measured
from the DSC trace, was 135 8C, which is in close
agreement with that reported in the literature for
AA2024 [1,19].
When 0.2%Sc was added to the 2024 base alloy,
changes were observed in the DSC traces, even though
no new phases were observed in the XRD results and the
as-cast microstructure appeared to be largely unaltered
(Fig. 2b). In Fig. 5 the higher temperature DSC peak at

/550 8C can be seen to be absent and the lower
temperature peak is now much broader. As no new
phases are formed for this low Sc level, it is thus likely
that the Sc addition has reduced the amount of solute
that is rejected during growth of the initial a-Al phase,
by changing the effective partition coefficient, such that
the liquid composition now intersects the univariant line
(U1 in Fig. 6a) closer to the ternary eutectic point (E1 in
Fig. 6a). This produces a single broader peak in the DSC
data, which on close inspection can be seen to contain a
shoulder and is thus made up of two overlapping peaks.
This double peak starts at
/510 8C, probably on
reaching the univariant line in the ternary system, before
terminating at
/500 8C, with the formation of the
ternary eutectic. As the final eutectic liquid to solidify
now freezes over a much narrower temperature range,
this should have the important result of reducing the
tendency for 2024 to exhibit solidification cracking.
When the Sc-free 2024 base alloy, and the alloys that
contained insufficient Sc to cause grain refinement (i.e.
B/0.6% Sc) were examined in the SEM (Fig. 7a), the a/
u and a/u/S eutectic, produced by the freezing
behaviour described above, was found to form an
almost continuous layer along their grain boundaries.
This combination of a large grain size and a continuous
eutectic grain boundary film, seen in the unrefined 0
/
0.2% Sc containing 2024 alloys, is thus clearly respon-
sible for the poor mechanical performance of the
castings, shown in Table 1.
With greater concentrations of Sc (0.4 and above),
more dramatic changes to the DSC curves were seen for
the 2024 alloys (Fig. 5). The DSC traces now show as
many as three separate peaks in the temperature range
520
/570 8C. Furthermore, two new phases were ob-
served on the XRD traces (Fig. 4). The first was
identified as being the L12 /Al3Sc phase involved in the
grain refinement process, which could only just be
resolved at Sc levels greater than 0.6%, and the second
was identified as the W phase. The W phase is known to
occur in the Al
/Cu
/Sc system, as a ternary compound
with a tetragonal crystal structure (a /0.86 nm, c /0.51
nm), and a stoichiometry of
/Al5.4
8Cu6.6
4Sc [9]. As
well as these two new phases, the XRD traces up to the
highest Sc level studied, of 0.8%, still showed diffraction
peaks associated with the S-Al2CuMg and u-Al2Cu
phases normally seen in the parent alloy, although their
reducing peak areas indicated that their volume frac-
tions were decreasing with increasing Sc level.
Unfortunately the quaternary Al
/Cu
/Mg
/Sc alloy
system has not yet been assessed, so rigorous conclu-
sions concerning freezing path changes in the Sc
 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
/198
Fig. 7. Examples of back scattered FEGSEM images of the 2024 Al-
alloy castings, showing; (a) the base alloy, and (b) 2024/0.8% Sc.
containing Al
/Cu
/Mg alloys cannot be reliably made
at this stage. However, it is clear from the XRD data
that the additional peak present in the DSC curves is
associated with a new phase reaction involving the W
phase. The approximate liquidus plan for the Al-rich
corner of the ternary Al
/Cu
/Sc alloy system is known
[9], and this is depicted in Fig. 6b. This shows that in this
simpler system, apart from the phase fields containing a-
Al and Al3Sc, there is a transitional peritectic at 572 8C
(L/a/Al3Sc 0/L/a/W) and a ternary eutectic reac-
tion at 546 8C, between a, W, and u. No ternary
compounds have been reported in the Al
/Mg
/Sc
system [9] and there is also a low level of Mg in the
2024 alloy, relative to its solubility in aluminium. The W
phase may, therefore, appear in the Sc containing 2024
alloy in a similar manner to in the Al
/Cu
/Sc system, i.e.
via a combination of transitional peritectic and ternary
eutectic reactions, which give rise to the extra peaks seen
on the DSC curve in Fig. 5.
Despite the difficulties in interpreting the DSC data
discussed above, the overall effect of the Sc additions on
the grain boundary eutectic films can be seen in the
SEM images in Fig. 7. In the example SEM image of the
alloy with the highest Sc level investigated (0.8%; Fig.
7b), it can be seen that the grain boundary eutectic
phases appear different compared with those in the 2024
Sc-free control alloy (Fig. 7a) and this is presumably
195
because some of the S and u has been replaced by the W
phase. However it is also noticeable that, for the higher
Sc content alloy, less GB-eutectic is present and the
eutectic films are no longer as continuous. This beha-
viour is due to a combination of the extreme grain
refinement caused by the Sc, which leads to an increase
in the grain boundary area, and the influence of Sc on
the solidification behaviour, which appears to reduce the
overall volume fraction of the eutectic by modifying the
effective partition coefficient. Both of these factors
would be expected to lead to an increase in the ductility
of a cast structure and explain the improved properties
observed for the Sc-refined 2024 castings seen in Fig. 5.
3.4.2. The 7475 alloy
The XRD trace for the 7475 base alloy is shown in
Fig. 8. The main phases that have been identified are a-
Al, h-MgZn2 and S-Al2CuMg, which are all expected
for an alloy of this composition [1,20]. Despite the fact
that Al
/Zn
/Mg
/Cu alloys are widely used by industry,
it is only recently that attempts have been made to fully
assess the quaternary equilibrium phase diagram [21],
making the interpretation of the DSC data more
difficult than for the 2024 alloy. A DSC trace of the
7475 alloy is shown in Fig. 9, and contains a very small
peak at 505 8C and a larger peak at
/470 8C, which is
most probably associated with the ternary eutectic
reaction between L, a, h and S (the main solidification
peak at
/640 8C is not shown on the plot). The smaller
high temperature peak, which occurs at
/505 8C,
cannot be explained at present. Nevertheless, the overall
freezing range measured by DSC, of
/165 8C, agrees
well with values published in the literature [1].
When Sc additions (in conjunction with 0.15% Zr and
0.12% Ti) were made to the 7475 alloy, no additional
phases could be found in the XRD data, apart from
Al3Sc which caused the remarkable levels of grain
refinement seen for Sc concentrations as low as 0.2%
(Fig. 8). In contrast to the behaviour of the 2024 alloy,
the presence of the W phase could not be detected for
Fig. 8. X-ray diffraction traces for the 7475 alloys showing the
presence of the h and S phases; in the Sc-free base alloy, and with
additions of 0.2 and 0.4% Sc.
196 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
/198

Fig. 9. DSC traces for the 7475 Al-alloy, showing the base alloy and
with additions of 0.1, 0.3 and 0.5% Sc. In all cases Sc was used in
conjunction with additions 0.12% Zr and 0.15% Ti.

the composition range investigated. However, for Sc

levels greater than 0.2% there was a significant reduction
in the peak area of the S and h phases, suggesting that
their volume fractions had reduced (Fig. 8). When the
DSC traces in Fig. 9 are compared for the different Sc
compositions, it appears that there is no significant
change in the position, or width, of the peak at 470 8C,
which is associated with the ternary a/S/h reaction.
In contrast, the small, unidentified, higher temperature
peak (initially present at
/505 8C) changes its position
with increasing Sc level, although the reasons for this
behaviour are not yet understood.
Overall, the results show that the level of Cu in the
7475 alloys investigated is too low to form the W phase
seen in the higher Cu content 2024 alloy. As mentioned
previously, in contrast to the Al
/Cu
/Sc system, there
are no known ternary compounds at the Al-rich end of
the Al
/Mg
/Sc system [9], and although the Al
/Zn
/Sc
phase diagram is as yet to be assessed, these results
indicate that Sc does not interact strongly with Zn in
dilute Al-alloys. Therefore, apart for the formation of
the Al3Sc phase, the solidification pathway of the 7475
alloy appears to remain largely un-altered as the Sc level
Fig. 10. Back scattered FEGSEM images of the 7475 series Al alloy
increases, with solidification terminating with the same castings, depicting in; (a) the base alloy, (b) 7475 with 0.2% Sc, and (c)
eutectic reaction at
/470 8C. However, in common 7475 with 0.4% Sc.
with the behaviour of the 2024 castings, the overall
volume fraction of the eutectic phases reduces as the Sc of that required to obtain grain refinement, a large
concentration increases. improvement in the ductility of the castings was
When the Sc-free 7475 alloy was examined in the obtained. When the alloy with this composition was
SEM (Fig. 10a), the large coarse columnar grains (seen examined in the SEM, it became apparent that for this
optically, Fig. 3a) were found to have an almost higher Sc level the grain boundary eutectic film had
continuous layer of eutectic along their grain bound- reduced in volume fraction and was no longer as
aries. Although the grain size was greatly refined after continuous, (Fig. 10c). This suggests, as was noted
an addition level of only 0.2% Sc (/ Ti &Zr) was made above from the XRD data, that the increased Sc level
to the alloy, it can be seen in Fig. 10b that the eutectic has led to improved tensile properties by reducing the
phases still formed a continuous film around the now volume fraction of the eutectic phases that are formed
fine equiaxed grains. This explains why, at this Sc level, during solidification, as well as by refining the grain size.
the tensile ductility remained low, despite the fact that It was also reported above, that higher levels of Sc than
the casting was grain refined. In contrast, when the Sc 0.4 wt.% tended to lead to a decline in ductility. This can
content was increased to 0.4%, which is slightly in excess be explained by the increase in volume fraction and size
 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
/198 197

of the primary Al3Sc particles as the Sc concentration
rises in the melt and implies that there is an optimum Sc
addition level of
/0.4 wt.% for a 7475 alloy.
Further evidence of the change in effective partition
coefficient, that causes a reduction in the volume
fraction of grain boundary eutectic with increasing Sc
content, is presented in Fig. 11. This figure shows
microprobe scans for the 7475 base alloy without Sc,
and for a 7475 casting containing 0.3% Sc. From Fig.
11, it can be seen that when Sc is present, the average
amount of Zn and Mg that is retained in solid solution
within a grain has substantially increased, from 4.4 to
6.2% for Zn, and 1.8 to 2.6% for Mg. This behaviour
confirms that Sc effectively reduces the partition coeffi-
cient during freezing and suggests that for the castings
that contained higher levels of Sc, the observed im-
provement in strength are also probably related to a
stronger natural ageing response (the samples were
tested 1 month after casting).
4. Conclusions
Simple wedge casting experiments have demonstrated
that it is possible to achieve exceptional grain refinement
in commercial aluminium aerospace alloys, at cooling
rates comparable to fusion welding, through the addi-
tion of the transition element scandium. The grain sizes

Fig. 11. Microprobe analysis across the centre of the 7475 castings, (a) without Sc and (b) with a 0.3% Sc addition level.
198 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
/198
achieved were particularly fine in the case of the 7000
alloy which, in conjunction with small Zr and Ti
additions, only required a 0.2%Sc level to obtain a grain
size of
/25 mm at 100 K s 1. Refinement occurs due to
the precipitation of cubic L12 Al3Sc phase, as primary
particles, once a critical Sc level has been achieved in the
melt. This phase nucleates aluminium grains at low melt
undercoolings and with a high nucleation efficiency,
which results in the grains impinging before they
develop a cellular or dendritic substructure.
In the 2024 aluminium alloy, additions of Sc caused
an interaction with Cu, resulting in a change in the
solidification pathway. It is suggested that in this alloy
the ternary eutectic reaction between L, a, u and S,
which normally occurs at
/500 8C, is replaced with
one or more higher melting point reactions, possibly
between L, a, u, S and W. This is in contrast to the 7475
castings, where, apart from grain refinement caused by
the Al3Sc primary particles, the addition of Sc did not
appear to significantly alter the normally expected
eutectic phases. However, in both alloys Sc changes
the effective partition coefficient and reduces the
amount of eutectic formed.
For both types of alloy, the reduction in the amount
of eutectic formed on solidification, coupled with an
increase in the grain boundary area due to grain
refinement, was sufficient to disrupt the eutectic films
that form at the grain boundaries during freezing. This
produced a significant increase in the alloys as-cast
tensile strength and ductility. Sc also appears to increase
the amount of solute retained in solid solution after
freezing which has the potential for increasing strength
through enhancing the as-cast ageing response.
In the context of welding, these results are important,
as it has been clearly demonstrated that Sc bearing filler
wires will help to both reduce the tendency for
solidification cracking in aluminium aerospace alloys,
and improve their weld metal properties.
Acknowledgements
This work was supported by the EPSRC under the
IMI Programme (GR/M2420), and is released with the
kind permission of the following partners: QinetiQ Ltd.,
BAE SYSTEMS, Short Brothers, Rolls Royce, Alcoa,
and TWI. Support from the Ministry of Defence
Corporate Research Programme is gratefully acknowl-
edged.
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