Materials Science and Engineering A354 (2003) 188
/198

www.elsevier.com/locate/msea

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

2000 series (e.g. 2014 and 2024), and Cu containing 7000
In recent years, the welding of aluminium aerospace- series alloys (e.g. 7475, 7150), as these materials tend to
alloys has received renewed attention, because of the have a wide freezing range and form low melting point
need to reduce the high manufacturing costs associated eutectic phases.
with the fabrication of riveted, or fastened, airframe Solidification cracking occurs when the thermal
structures. However, many of the Al-alloys that are stresses that build up during freezing exceed the strength
currently used in aircraft are considered to be not of the solidifying weld metal [2,4]. Methods that are
recommended for fusion welding [1,2]. Particular pro- commonly used to reduce the tendency for solidification
blems that limit their weldability, include: solidification cracking include: altering the weld composition, through
cracking within the fusion zone, liquation cracking at the addition of a filler wire, close process control, and
the boundary between the fusion zone and the HAZ, controlling the grain structure within the fusion zone
and poor corrosion performance [1
/3]. These problems [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,
* Corresponding author. Present address: Corus RD & T, Swinden and the remaining eutectic liquid present during the final
Technology Centre, Moorgate, Rotherham S60 3AR, UK. Tel.: /44-
1709-82-5318; fax: /44-1709-82-5337.
stages of solidification can feed more easily, and heal
E-mail address: [email protected] (A.F. Norman). 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
/198 189

Another important drawback to fusion welding 2000 freezing paths of the alloys. This second aspect of the
and 7000 series alloys is their poor fusion zone strength work is important, as little is currently known about
and ductility. This is a particular problem for compo- how Sc interacts with multi-component commercial Al-
nents containing unreinforced welds, and in aerospace alloys. To gain an insight into the performance of the Sc
structures, good strength levels are required to obtain a modified solidification structures, and to assess the
high joint efficiency. Unfortunately, commercially avail- effect of Sc on potential weld fusion zone properties,
able Al-filler wires have not been specifically developed the tensile behaviour of the castings was studied as a
for aerospace alloys and currently provide insufficient function of the Sc content and cooling rate. Relation-
strength for many applications. In some cases the joint ships between the freezing behaviours and properties of
strength levels can be as low as 50% of the parent the Sc containing alloys are then discussed.
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 2. Experimental
7050.
The alloy addition Sc has recently become of con- The different alloy compositions used in this study
siderable interest to the aluminium welding community, were prepared using master alloys and commercial
as it has been claimed that small concentrations of Sc purity Al (99.7%). The Sc-free baseline alloys had
can produce enhanced weldability in Al-alloys that are nominal compositions approximately equivalent to,
susceptible to solidification cracking and can also AA2024 and AA7475, of Al
/4.5%Cu
/1.5%Mg and
improve their weld metal strengths [6]. The original Al
/5.5%Zn
/2.2%Mg
/1.5%Cu, respectively. These al-
research on Sc additions to aluminium was carried out loys are referred to as 2024 and 7475 below. Sc
in the former Soviet Union (e.g. [7
/9]). More detailed additions were made to the melts using an Al
/2%Sc
studies of the solidification behaviour of Al
/Sc alloys master alloy, to give concentrations from 0 to 0.8 wt.%
have now been published in the West and confirm many Sc. Sc was added either on its own, or in conjunction
of the earlier observations made by Russian scientists with 0.12% Ti and 0.15% Zr (see below for details). The
(e.g. [10
/12]). However, to date, this information has different alloy compositions were cast into a wedge-
mainly been limited to simple alloy systems. Further- shaped mould, that produced cooling rates from 10 K
more, the limited published work that has claimed s 1, at the top of the mould, to 100 K s 1 near the
substantial improvements in the properties of Sc con- wedge tip. The cooling rate at the wedge tip was,
taining fusion welds, has not provided optimised therefore, similar to that found in TIG and MIG weld
compositions or investigated in detail the underlying pools [10]. After casting, each alloy was analysed using
mechanisms as to why such improvements are found wet chemical analysis to verify that the actual composi-
(e.g. [6
/9,13]). tions fell close to the nominal compositions, specified
The long-term aim of the current research programme above. It should be noted that the Sc-free baseline
at Manchester is to develop a new generation of Sc castings did not contain Ti/TiB2. All the compositions
containing filler wires that will improve the weldability given here and below are quoted as weight percentages.
of 2000 and 7000 series Al aerospace alloys. However, After casting, sections were taken from three positions
the manufacture of filler wires is a time consuming and along the centreline of each wedge casting, which
expensive process. Therefore, to minimise the number of corresponded to different cooling rates (the top, centre
experimental wire compositions that are required, small and tip). To reveal the grain structure for optical
wedge shaped castings have been used as a method of metallography, the samples were anodised in Barkers
simulating the cooling rates, typically found in the reagent and examined under polarised light. For SEM
fusion zones of MIG and TIG welding processes. By examination, samples were lightly electropolished and
using this approach, and adding a range of Sc levels to subsequently examined in a Philips FEGSEM, operated
the alloys of interest, potential optimum filler composi- at 10 kV. Cylindrical tensile specimens were machined
tions can be rapidly identified that can subsequently be from the same three locations in the castings, with a
made into wire and tested (the results of the welding gauge diameter of 6 mm and a gauge length of 50 mm,
trials obtained with the filler wire compositions identi- and tested at an applied strain rate of
/103 s 1, 1
fied from this investigation will be the subject of another month after casting. Grain size measurements were
publication [14]). The two parent alloys selected for made using the mean linear intercept method [15].
investigation were based on (i) AA2024 and (ii) AA7475, DSC measurements were made using a Netzsch 204
which are typical examples of commonly used 2000 and and a Perkin
/Elmer Pyris 1 DSC. For each composition
7000 series aerospace alloys. Metallography was used to studied, between 20 and 80 mg of material was melted in
investigate the ability of Sc to refine the fusion zone the DSC pan and cooled from above the liquidus
grain structures, whereas DSC and XRD were used to temperature, at a rate of 10 8C min 1 in an argon
study the effect of Sc on the phase formation and atmosphere.
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3. Results and discussion Al. For hypoeutectic compositions (containing less than
0.55% Sc), on cooling from the liquid, the first phase to
3.1. The solidification behaviour of binary Al
/Sc alloys form is a-Al and, and when no external grain refiners
are used, the grain structure on solidification is coarse,
Before considering the interaction of Sc with the more as might be expected in most conventional alloys (Fig.
complex alloys of prime interest, it is useful to first 1b). However, when the Sc level exceeds the eutectic
summarise results that have previously been reported for point, on crossing the liquidus the L12 Al3Sc phase
the solidification behaviour of the simpler binary Al
/Sc precipitates first from the melt, as small cubic primary
system [10]. The Al-rich end of the Al
/Sc equilibrium particles [11]. Due to the close similarity between the L12
phase diagram, shown in Fig. 1a [16], is dominated by a crystal structure and the FCC a-Al matrix, and the small
eutectic reaction between L, a and Al3Sc. The equili- lattice mismatch (
/1.5%), the Al-3Sc particles act as
brium Al3Sc phase has an ordered L12 cubic crystal excellent nucleation sites for a-Al grains [9,10], resulting
structure, and the eutectic point occurs at 0.55% Sc and in a very high level of grain refinement (Fig. 1c). In a
655 8C, which is only 10 8C below the melting point of 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
Fig. 1. (a) The Al-rich end of the Al
/Sc equilibrium phase diagram
primary particles could be seen at the centre of some
[16]. Examples of typical cast microstructures for a hypoeutectic Al
/
0.2% Sc alloy, showing a large columnar dendritic grain structure, and grains, indicating that the grain refining mechanism is
a hyper eutectic Al
/0.7% Sc alloy, showing highly refined equiaxed similar to that found in the binary system. However,
grains with no sub-structure, are given in (b) and (c), respectively. primary Al3Sc particles were also commonly observed at
 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
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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 that seen when 0.6% Sc was used without Ti and Zr (Fig.
freezing and had presumably not taken part in the 2d).
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 3.2.2. The 7475 alloy
reduce the amount of Sc required to achieve grain The microstructure of the Sc-free 7475 alloy casting
refinement, as well as the overall grain size. This is was very similar to that seen with the Sc-free 2024
thought to occur because Zr and Ti can substitute for Sc control alloy, and was again comprised of very large
in the Al3Sc phase, and is obviously advantageous grains with a dendritic substructure (Fig. 3a). Since the
because of the relatively high cost of Sc. To verify beneficial effects of using combined additions of Sc with
whether this effect would also take place in a 2000 series Zr and Ti, found with the 2024 alloy, in the case of the
alloy, further castings were made that included additions 7475 alloy, Sc additions were always made in conjunc-
of 0.12Zr and 0.15Ti (these levels were chosen because tion with the same fixed level of 0.12% Zr and 0.15% Ti.
they are the maximum that can normally be used in a Sc- However, in this case, grain refinement was observed
free Al-alloy without forming primary particles). When when a concentration of as little as 0.2% Sc was reached
Zr and Ti were added to the base alloy, the minimum in the castings, (Fig. 3b) as opposed to the higher
amount of Sc required to produce grain refinement was concentration of 0.4% required for the 2024 alloy (when
indeed reduced, to 0.4% Sc, as can be seen in Fig. 2e. Ti and Zr were present). Furthermore, even with this
However, the refined grain size was still very similar to lower Sc level, the refined grain size was considerably
192 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
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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 are given in Table 1 and, for the 2024 alloys, show that
to 40 mm at the tip of the castings (Fig. 2e, Fig. 3b). when the Sc level was too low to exhibit a refined grain
When greater additions of Sc, than the minimum structure (B/0.6% Sc) tensile strengths of 170
/200 MPa
required for refinement, were made to the 7475 casting were typical. These compositions also exhibited almost
the grain size continued to slowly reduce. For example, zero ductility, as might be expected from castings having
at the mould tip the grain size decreased from
/25 mm, a very large grain size and containing grain boundary
with 0.2% Sc (Fig. 3c), to as small as
/15 mm for a 0.8% eutectic phases (see below, Section 3.4). In sharp
Sc concentration (Fig. 3e). It should be emphasised at contrast, those alloys which contained sufficient addi-
this stage that these are extremely fine grain sizes for tions of Sc to refine the grain size produced an increase
aluminium castings, that cannot normally be achieved in strength of
/100 to around 300 MPa. More
significantly, these alloys showed reasonable ductilities,
using conventional grain refiners such as Ti/TiB2.
for an as-cast 2024 structure, of 3
/5%. This is higher
than the level of ductility that is usually observed in
3.3. Tensile properties of the castings conventional Sc-free MIG or TIG welds with a similar
alloy composition [5].
3.3.1. The 2024 alloy
Tensile tests were performed on specimens machined 3.3.2. The 7475 alloy
from the tip, centre, and close to the top surface of the The unrefined 7475 Sc-free casting also had poor
wedge-shaped castings, giving data for a range of mechanical properties (Table 1), with a tensile strength
cooling rates. The resultant tensile properties measured 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 Al2Cu and S-Al2CuMg (see Fig. 4). A DSC trace taken
and 0.15% Ti), the strength increased to
/ 300 MPa, from the 2024 alloy is shown in Fig. 5 and contains two
although, at 0.5%, the ductility of this casting was only peaks, one at
/550 8C and the other at
/500 8C,
slightly better than the base alloys. This poor elonga- apart from the main solidification exotherm at 640 8C
tion occurred despite the fact that there was sufficient Sc (L 0/L/a-Al) which is not shown on the trace. The
in the alloy to produce a greatly refined grain structure liquidus plan for the ternary Al
/Cu
/Mg alloy system,
(see Fig. 3b). However, when the Sc level was increased calculated using MTDATA and the COST507 light alloys
to 0.4%, the ductility of the casting increased substan- data base [18], is depicted in Fig. 6a. According to this
tially and the strength also rose further, giving an diagram, for an alloy with the same Cu and Mg content
elongation of 4% and a tensile strength of 380 MPa at as 2024 (4.5% Cu, 1.5% Mg), on freezing the first phase
the wedge tip. Although there is some scatter in the data, to form from the liquid is a-Al and this gives rise to the
it was noticeable that at higher addition levels than 0.4% main solidification peak seen on crossing the liquidus at
Sc there was a trend for the castings ductilities to
/640 8C. As solidification proceeds, solute is rejected
decline (this is most apparent at the wedge tip in Table and the liquid Cu and Mg concentration increases, until
1). the univariant line (U1 in Fig. 6a) is reached. This point
is coincident with the 550 8C peak on the DSC trace
3.4. Phase formation during solidification (Fig. 5). Below this temperature, a-Al and u-Al2Cu
solidify simultaneously as a eutectic, and the liquid
To fully explain the relationships between the im- composition subsequently follows the univariant line
provement in tensile properties and the Sc concentration until the ternary eutectic reaction is reached, at E1 (see
in the different castings (which did not necessarily Fig. 6a). The final liquid then solidifies isothermally, via
coincide exactly with the minimum Sc level required this ternary eutectic reaction, to form a-Al, u-Al2Cu,
for grain refinement), DSC, XRD and SEM analysis and S-Al2CuMg, amd corresponds to the lowest tem-
were performed on samples taken from the centre of perature peak seen on the DSC trace at
/505 8C (Fig.
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).

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
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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
Fig. 5. DSC traces showing the 2024 base alloy, and 2024 plus Sc (U1 in Fig. 6a) closer to the ternary eutectic point (E1 in
levels of 0.2, 0.4, 0.6 and 0.8% Sc.
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
Fig. 6. Liquidus plans for, (a) the Al
/Cu
/Mg alloy system, calculated
peaks associated with the S-Al2CuMg and u-Al2Cu
using MTDATA [18], and (b) the Al-rich corner of the Al
/Cu
/Sc alloy
system (adapted from [9]). phases normally seen in the parent alloy, although their
reducing peak areas indicated that their volume frac-
5). The overall melting range of the base alloy measured tions were decreasing with increasing Sc level.
from the DSC trace, was 135 8C, which is in close Unfortunately the quaternary Al
/Cu
/Mg
/Sc alloy
agreement with that reported in the literature for system has not yet been assessed, so rigorous conclu-
AA2024 [1,19]. sions concerning freezing path changes in the Sc
 A.F. Norman et al. / Materials Science and Engineering A354 (2003) 188
/198 195

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
Fig. 7. Examples of back scattered FEGSEM images of the 2024 Al- peak at 505 8C and a larger peak at
/470 8C, which is
alloy castings, showing; (a) the base alloy, and (b) 2024/0.8% Sc. most probably associated with the ternary eutectic
reaction between L, a, h and S (the main solidification
containing Al
/Cu
/Mg alloys cannot be reliably made peak at
/640 8C is not shown on the plot). The smaller
at this stage. However, it is clear from the XRD data high temperature peak, which occurs at
/505 8C,
that the additional peak present in the DSC curves is cannot be explained at present. Nevertheless, the overall
associated with a new phase reaction involving the W freezing range measured by DSC, of
/165 8C, agrees
phase. The approximate liquidus plan for the Al-rich well with values published in the literature [1].
corner of the ternary Al
/Cu
/Sc alloy system is known When Sc additions (in conjunction with 0.15% Zr and
[9], and this is depicted in Fig. 6b. This shows that in this 0.12% Ti) were made to the 7475 alloy, no additional
simpler system, apart from the phase fields containing a- phases could be found in the XRD data, apart from
Al and Al3Sc, there is a transitional peritectic at 572 8C Al3Sc which caused the remarkable levels of grain
(L/a/Al3Sc 0/L/a/W) and a ternary eutectic reac- refinement seen for Sc concentrations as low as 0.2%
tion at 546 8C, between a, W, and u. No ternary (Fig. 8). In contrast to the behaviour of the 2024 alloy,
compounds have been reported in the Al
/Mg
/Sc the presence of the W phase could not be detected for
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 Fig. 8. X-ray diffraction traces for the 7475 alloys showing the
phases appear different compared with those in the 2024 presence of the h and S phases; in the Sc-free base alloy, and with
Sc-free control alloy (Fig. 7a) and this is presumably 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 cient during freezing and suggests that for the castings
rises in the melt and implies that there is an optimum Sc that contained higher levels of Sc, the observed im-
addition level of
/0.4 wt.% for a 7475 alloy. provement in strength are also probably related to a
Further evidence of the change in effective partition stronger natural ageing response (the samples were
coefficient, that causes a reduction in the volume tested 1 month after casting).
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, 4. Conclusions
and for a 7475 casting containing 0.3% Sc. From Fig.
11, it can be seen that when Sc is present, the average Simple wedge casting experiments have demonstrated
amount of Zn and Mg that is retained in solid solution that it is possible to achieve exceptional grain refinement
within a grain has substantially increased, from 4.4 to in commercial aluminium aerospace alloys, at cooling
6.2% for Zn, and 1.8 to 2.6% for Mg. This behaviour rates comparable to fusion welding, through the addi-
confirms that Sc effectively reduces the partition coeffi- 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 BAE SYSTEMS, Short Brothers, Rolls Royce, Alcoa,
alloy which, in conjunction with small Zr and Ti and TWI. Support from the Ministry of Defence
additions, only required a 0.2%Sc level to obtain a grain Corporate Research Programme is gratefully acknowl-
size of
/25 mm at 100 K s 1. Refinement occurs due to edged.
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,
References
which results in the grains impinging before they
develop a cellular or dendritic substructure. [1] J.R. Davis (Ed.), ASM Speciality Handbook: Aluminium and
In the 2024 aluminium alloy, additions of Sc caused Aluminium Alloys, ASM International, Metals Park, OH, 1993.
an interaction with Cu, resulting in a change in the [2] S. Kou, Weld. Res. Coun. Bull. 320 (1986) 1.
solidification pathway. It is suggested that in this alloy [3] D.E. Schillinger, I.G. Betz, F.W. Hussey, H. Markus, J. Weld. 42
the ternary eutectic reaction between L, a, u and S, (1963) 269S.
[4] S.A. David, J.M. Vitek, Int. Mater. Rev. 34 (1989) 213.
which normally occurs at
/500 8C, is replaced with
[5] N.J. Woodward, I.M. Richardson, A. Thomas, Sci. Technol.
one or more higher melting point reactions, possibly Weld. Joining 5 (2000) 21
/25.
between L, a, u, S and W. This is in contrast to the 7475 [6] B. Irving, Weld. J. 76 (1997) 53.
castings, where, apart from grain refinement caused by [7] I.I. Novikov, O.E. Grushko, Mater. Sci. Technol. 11 (1995) 926.
the Al3Sc primary particles, the addition of Sc did not [8] V.G. Davydov, V.I. Yelagin, V.V. Zakharov, Y.A. Filatov,
Mater. Sci. Forum 217 (1996) 1841.
appear to significantly alter the normally expected
[9] L.S. Toropova, D.G. Eskin, M.L. Kharakterova, T.V. Dobat-
eutectic phases. However, in both alloys Sc changes kina, Advanced Aluminium Alloys Containing Scandium, Gor-
the effective partition coefficient and reduces the don and Breech, The Netherlands, 1998.
amount of eutectic formed. [10] A.F. Norman, R. McEwen, P.B. Prangnell, Acta Mater. 46 (1998)
For both types of alloy, the reduction in the amount 5715.
of eutectic formed on solidification, coupled with an [11] K. Hyde, A.F. Norman, P.B. Prangnell, Acta Mater. 49 (2001)
1327.
increase in the grain boundary area due to grain [12] M.G. Mousavi, C.E. Cross, . Grong, Sci. Technol. Weld.
refinement, was sufficient to disrupt the eutectic films Joining 4 (1999) 381.
that form at the grain boundaries during freezing. This [13] L.S. Kramer, W.T. Tack, M.T. Fernandes, Adv. Mater. Processes
produced a significant increase in the alloys as-cast 152 (1997) 23.
tensile strength and ductility. Sc also appears to increase [14] A.F. Norman, S.S. Birley, P.B. Prangnell, Sci. Technol. Weld.
Joining, in press.
the amount of solute retained in solid solution after
[15] F.B. Pickering, Basis of Quantitative Metallography, Institute of
freezing which has the potential for increasing strength Metals, London, UK, 1975.
through enhancing the as-cast ageing response. [16] K.A. Gschneidner, F.W. Calderwood, Bull. Alloy Phase Diag. 10
In the context of welding, these results are important, (1989) 34.
as it has been clearly demonstrated that Sc bearing filler [17] S.V. Inkin, A.V. Kurdyumov, V.I. Napalkov, D.M. Pankratov,
wires will help to both reduce the tendency for A.A. Semenchenkov, Tekhnologiya Liogkikh Splavov (Russian) 4
(1990) 52.
solidification cracking in aluminium aerospace alloys, [18] R.H. Davies, A.T. Dinsdale, T.G. Chart, T.I. Barry, M.H. Rand,
and improve their weld metal properties. High Temp. Sci. 26 (1988) 251.
[19] L.F. Mondolfo, Aluminium Alloys: Structure and Properties,
Butterworths, London, 1976, p. 497.
Acknowledgements [20] D.S. MacKenzie, Seventh International Seminar of IFHT (Inter-
national Federation for Heat Treatment and Surface Engineer-
ing), Budapest, Hungary, 15
/17 September 1999.
This work was supported by the EPSRC under the [21] H.J. Seifert, P. Liang, H.L. Lukas, F. Aldinger, S.G. Fries, M.G.
IMI Programme (GR/M2420), and is released with the Harmelin, F. Faudot, T. Jantzen, Mater. Sci. Technol. 16 (2000)
kind permission of the following partners: QinetiQ Ltd., 1429.