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Materials Science and Engineering A 462 (2007) 370–374

Annealing effects in Al–Sc alloys


B. Smola a,∗ , I. Stulı́ková a , V. Očenášek b , J. Pelcová a , V. Neubert c
a Charles University, Faculty of Mathematics and Physics, Ke Karlovu 5, 121 16 Prague 2, Czech Republic
b Research Institute of Metals, Panenské Břežany 50, 250 70 Odolena Voda, Czech Republic
c Zentrum für Funktionswerkstoffe, Sachsenweg 8, 38678 Clausthal-Zellerfeld, Germany

Received 30 August 2005; received in revised form 28 October 2005; accepted 5 November 2005

Abstract
Al–0.5Sc–0.4Zr and Al–2.7Mg–0.14Sc–0.045Zr alloys (numbers indicate wt.%) were prepared by powder metallurgy. Both materials contained
a fine dispersion of spherical Al3 (Sc1−x Zrx ) particles, which developed during extrusion at 350 ◦ C. Cold and hot rolling of the as extruded
Al–2.7Mg–0.14Sc–0.045Zr alloy influence the isochronal electrical resistivity annealing curves. The relative resistivity changes measured reflect
recovery of the dislocation structure as well as precipitation and dissolution of ␤ , ␤ and/or ␤ phases of the Al–Mg system and the Al3 (Sc1−x Zrx )
phase. Precipitation of very fine Guinier–Preston zones or particles of the ␤ phase increase the resistivity of both as-extruded and cold rolled
Al–2.7Mg–0.14Sc–0.045Zr alloy. Despite recovery of dislocations in the cold rolled Al–2.7Mg–0.14Sc–0.045Zr alloy between 150 and 180 ◦ C,
isochronal annealing curves of hardness HV10 show that very good mechanical properties persist up to 350 ◦ C due to the stability of Al3 (Sc1−x Zrx )
phase particles.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Al alloys; Scandium; Magnesium; Electrical resistivity; Isochronal annealing

1. Introduction As the solubility of Sc in Al is very low (∼0.22 at.% at the eutec-


tic temperature of 655 ◦ C [1,12]) the high cooling rate during
The small addition of Sc to aluminium and aluminium alloys solidification of Sc containing Al alloys is essential to prevent
(up to ∼0.5 wt.%) increases the recrystallisation temperature the precipitation of primary Al3 Sc phase particles which can
markedly and has a beneficial effect on mechanical proper- inhibit the desirable age hardening. Powder production as one
ties, weldability and corrosion resistance [1–4]. Combination of the rapid solidification methods can be more successful, as
of small additions of Sc and Zr even enhances the strengthening compared to the conventional casting methods.
effect on mechanical properties by preserving an intense initial The aim of the present paper is to study phase trans-
nucleation and suppressing the succeeding coarsening of fine formations, microstructure and hardening in Al–Sc–Zr and
coherent Al3 (Sc1−x Zrx ) phase particles [1,3,5]. Al–Mg–Sc–Zr alloys prepared by the PM method.
The possibility of age hardening introduced by minor addi-
tions of other elements is of special interest in Al–Mg wrought 2. Experimental
alloys. These alloys exhibit reasonable solid solution hardening,
but only poor age hardening due to the kinetics of the supersat- A dilute Al–Sc–Zr alloy (0.5 wt.% Sc, 0.3 wt.% Zr) and
urated solid solution (s.s.s.) decomposition [1,6]. Consequently, Al–Mg–Sc–Zr (composition in Table 1) were prepared by
there is a continuous interest in improving further the properties squeeze casting. Powder from these alloys was produced by
of Al–Mg alloys by the addition of Sc and Zr [3,4,7–10]. About atomising in a stream of inert gas [11]. The size of the pow-
900 papers dealing with Sc containing aluminium alloys have der particles was about 30 ␮m. The powder was consolidated
been published since 1971, but only a single one is devoted to by extrusion at 350 ◦ C. The as extruded Al–Sc–Zr alloy was
the production of these alloys by powder metallurgy (PM) [11]. annealed at 550 ◦ C for 20 min and was subsequently water
quenched to check the possibility of the dissolution of the phases
precipitated during the production.
∗ Corresponding author. Tel.: +420 221 911 355; fax: +420 221 911 618. The isochronal annealing response of the relative resistivity
E-mail address: bohumil.smola@mff.cuni.cz (B. Smola). changes ρ/ρ0 was determined in the range of 20–540 ◦ C in

0921-5093/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2005.11.075
B. Smola et al. / Materials Science and Engineering A 462 (2007) 370–374 371

Table 1
Composition of the Al–Mg–Sc–Zr alloy
Mg Sc Zr Fe Si

wt.% 2.690 0.140 0.045 0.110 0.094


at.% 2.981 0.084 0.013 0.053 0.090

order to map the temperature ranges of phase transformations.


The isochronal annealing, carried out in steps of 30 K/30 min,
was followed by quenching after each step. Heat treatment was
performed in a stirred oil bath up to 240 ◦ C or in a furnace with
an argon protective atmosphere at higher temperatures. Electri-
cal resistivity was measured at −196 ◦ C after each heating step.
Relative resistivity changes ρ/ρ0 were obtained to an accuracy Fig. 1. Dynamically recovered substructure of Al–Mg–Sc–Zr alloy after extru-
of 10−4 by means of the direct-current four-point method with a sion at 350 ◦ C. Dark-field weak-beam image in (1 1 1)Al reflection.
dummy specimen in series. The effect of parasitic thermoelec-
tromotive force was suppressed by change of polarity. Electrical
resistivity was measured also at 20 ◦ C for selected states of the diameter) and it resulted in the formation of denuded zones
material. The ratio RRR = ρ(20 ◦ C)/ρ(−196 ◦ C) does not depend along the sub-grain boundaries. The anti-recrystallisation effect
on a specimen form-factor and increases with increasing effec- of Sc and the decomposition kinetics of the s.s.s. of PM pro-
tive material purity. duced Al–Sc–Zr alloy are similar to those in continuously cast
Changes in Vickers hardness HV10 due to the heat treatment Al–Sc–Zr alloys [3,14].
described were also monitored to reveal the thermal stability
of the mechanical properties as related to the microstructural
development.
Transmission electron microscopy, electron diffraction (ED)
and energy dispersive X-ray microanalysis (EDX) were used
to determine the structure and morphological characteristics of
the phases precipitated (JEOL JEM 2000FX electron micro-
scope and Link AN 10000 micro-analyser). The specimens
for transmission electron microscopy were treated by the same
isochronal annealing procedure as those for electrical resistivity
and hardness measurements.

3. Results and discussion

3.1. Microstructure of as extruded alloys

Both alloys investigated show the dynamically recovered sub-


structure in the as extruded state, see Fig. 1. Grain (sub-grain)
size is in the range from 0.5 to 1.5 ␮m; the grains are elon-
gated along the extrusion direction. Homogeneous precipitation
of fine coherent spherical particles of the Al3 (Sc1−x Zrx ) phase
(L12 , cP4 structure, a ≈ aAl ) took place during the extrusion
process at 350 ◦ C—Fig. 2. The diameter of the particles in both
alloys studied ranges between 2 and 6 nm. The volume frac-
tion of the phase was estimated to be ∼0.004 in the Al–Sc–Zr
alloy. This precipitation process is similar to that of the die cast
Al–0.39 wt.%Sc–0.29 wt.%Zr alloy during isothermal anneal-
ing at 300, 350 and 400 ◦ C [13]. Coarser Al3 (Sc1−x Zrx ) phase
particles decorate the grain (sub-grain) boundaries.
Annealing of as extruded Al–Sc–Zr alloy at 550 ◦ C for 20 min
has proved the anti-recrystallisation effect of the Al3 (Sc1−x Zrx )
phase. The sub-grain size increased only slightly to about
1.0–1.8 ␮m. Coarsening of spherical Al3 (Sc1−x Zrx ) phase parti- Fig. 2. Al3 (Sc1−x Zrx ) phase particles in prepared Al–Sc–Zr alloy after extrusion
cles in the grain (sub-grain) interior took place (to about 5–15 nm at 350 ◦ C. Dark-field image in (1 0 0) reflection of particles.
372 B. Smola et al. / Materials Science and Engineering A 462 (2007) 370–374

Fig. 3. Isochronal annealing curves of relative electrical resistivity changes


(open symbols) and of relative hardness HV10 (filled symbols) of the as extruded
state (AE, ) and after rolling at room temperature (CR, ) and at 300 ◦ C (HR,
♦).
Fig. 4. Fine particles in as extruded Al–Mg–Sc–Zr alloy (AE) after isochronal
annealing up to 360 ◦ C. Bright-field image in (2 0 0)Al reflection, see inset.
3.2. Resistivity changes and microstructural development
in the Al–Mg–Sc–Zr alloy
The scattering of conduction electrons at very small particles
The response of the relative electrical resistivity changes or clusters (e.g. Guinier–Preston zones) can lead to an increase
ρ/ρ0 of PM produced Al–Mg–Sc–Zr alloy to isochronal in electrical resistivity in the Al–Mg system [15]. The precip-
annealing (annealing curve) is dependent on the treatment itation of these particles occurred, most probably, already in
history—Fig. 3. The resistivity of the as extruded alloy (AE) the hot-rolled (HR) specimen during hot rolling at 300 ◦ C, but
increases from about 200 ◦ C to a maximum at 360 ◦ C and not in the cold-rolled (CR) specimen. Consequently, resistivity
decreases again almost to a zero change at 450 ◦ C. This is fol- measurement of the HR specimen cannot detect such a precipita-
lowed by a further increase at higher temperatures. tion during isochronal annealing in the temperature range below
The alloy which was hot rolled at 300 ◦ C after extrusion 300 ◦ C.
(HR) shows a relative resistivity, which decreases slowly up The precipitation of these particles in the CR alloy can take
to ∼300 ◦ C and then drops to a minimum at 450 ◦ C and then it place at lower temperatures than in the as-extruded (AE) alloy
increases again with increasing temperature. as diffusion is enhanced by the higher dislocation density there.
The behaviour of relative resistivity of PM produced Therefore, also their dissolution can start at lower temperatures
Al–Mg–Sc–Zr alloy after extrusion and rolling at room tem- in the CR alloy. The decrease in resistivity to the minima in
perature (CR) is similar to that of HR alloy except for the local both specimens, CR and AE at 450 ◦ C, should be ascribed to
minimum at 180 ◦ C. the dissolution of these fine particles at the beginning of the
The microstructure of CR and HR specimens differ mainly decrease and to the precipitation of new phases later on. This
in the dislocation density and the substructure. The CR alloy leads to the effective purification of the major phase determining
exhibits a high dislocation density and substructure characteris- the resistivity, i.e. the Al matrix.
tic of cold worked material. On the other hand, the HR specimen The shape of the minima in annealing curves of AE, CR
shows a lower dislocation density and substructure correspond- and HR specimens indicate the contribution of two precipi-
ing to the partial dynamical recovery. A diffraction response tation processes. It is even more evident from the shape of
of the L12 structure was detected neither in CR nor in the HR the spectrum curves (temperature derivative of the annealing
alloy, most probably due to the misorientation of Al3 (Sc1−x Zrx ) curve) – see Fig. 5. Single stages of the relative resistivity devel-
particles from cube to a cube relationship during rolling. Nev- opment can be fitted by Gaussian curves – for CR alloy see
ertheless, the fine spherical particles are pinning dislocations in Fig. 6.
the interior of sub-grains and in sub-boundaries in the HR spec- Calculations of the equilibrium state diagram of the ternary
imen. The most probable presence of these particles in the CR Al–Mg–Sc alloy [16] showed the possibility of precipitation of
specimen cannot be proved due to the high dislocation density, the stable Al3 Mg2 phase in Al–3 wt.%Mg–0.2 wt.%Sc alloy in
which masks and obscures their weak contrast. the temperature range under 200 ◦ C. The Sc addition can, there-
Microstructural development due to isochronal annealing fore decrease the solubility of Mg in Al. We ascribe the precipi-
was monitored by TEM in CR and AE alloys. The local mini- tation of fine particles, which increase the resistivity to some of
mum of the relative resistivity at 180 ◦ C in CR specimens can be the pre-precipitation processes known in the Al–Mg system (GP
attributed to the decrease in dislocation density. The subsequent zones, ␤ phase) [17]. The decrease in resistivity to a minimum
increase up to 270 ◦ C can be ascribed to the same processes, at 450 ◦ C can be interpreted as the sequence of the dissolution
which are responsible for the increase in the AE specimen of the fine particles mentioned above (∼305 ◦ C), precipitation
(to a maximum at 360 ◦ C). Very small particles giving typical of transient ␤ (hexagonal Al3 Mg2 ) or stable ␤ (complex f.c.c.
black–white contrast were detected in the AE specimen, which Al3 Mg2 ) phase (∼375 ◦ C) and precipitation (and/or coarsening)
had been isochronally annealed up to 360 ◦ C—Fig. 4. of stable Al3 (Sc1−x Zrx ) phase (∼434 ◦ C).
B. Smola et al. / Materials Science and Engineering A 462 (2007) 370–374 373

Fig. 5. Differential curves of relative electrical resistivity of as extruded (AE,


), cold rolled (CR, ) and hot rolled (HR, ♦) Al–Mg–Sc–Zr alloy.
Fig. 7. Coherent coffee-bean contrast of Al3 (Sc1−x Zrx ) phase particles in cold
rolled (CR) Al–Mg–Sc–Zr alloy after annealing up to 450 ◦ C. Dark-field image
The position of the precipitation stage of the fine particles in (2 2 0)Al reflection, see inset.
is shifted to a higher temperature in the AE alloy and stages of
their dissolution and precipitation of ␤ or ␤ phases overlap there.
Only Al3 (Sc1−x Zrx ) spherical particles were detected by TEM perature (350 ◦ C)—Fig. 3. The HV10 is high after extrusion
and ED in the CR and AE alloys annealed up to 450 ◦ C—Fig. 7. (equalling 105 in the as extruded alloy) and increases to 114
They are coherent and only slightly coarsened (diameter ∼8 to during hot rolling and to 118 by cold rolling. The fine disper-
∼20 nm). The Mg containing phase could not be identified, as its sion of the Al3 (Sc1−x Zrx ) phase particles precipitated during
contribution to the diffraction was not detected. Nevertheless, the extrusion ensures a high hardness up to about 350 ◦ C. In CR and
effect of purifying the matrix by precipitation and increasing the HR specimens the hardness decreased by only a few percent in
solute content during dissolution is strong enough to be detected this temperature range due to a decrease in dislocation density
by resistivity change measurements. and substructure recovery. At higher annealing temperatures,
An increase in resistivity from the minima at 450 ◦ C is caused the HV10 decreases continuously in all specimens of the alloy.
by the dissolution of Al3 Mg2 and Al3 (Sc1−x Zrx ) phases which This indicates a very low volume fraction and/or small strength
increases the concentration of solutes in the Al-matrix in all three of Mg containing particles. The decrease in hardness is mainly
specimens. The resistivity changes fully correspond to the possi- connected with coarsening and subsequent partial dissolution of
ble Mg and Sc concentration changes in the matrix as calculated Al3 (Sc1−x Zrx ) particles. Recent measurements of the Al–Sc–Zr
using values of contribution of 1 at.% of solute to the resistivity alloy resistivity in the same isochronal annealing procedure
of Al (∼5.7 n m for Mg and ∼35.8 n m for Sc, [18] and [1], yielded similar annealing curves to those of the Al–Mg–Sc–Zr
respectively). alloys with ∼12% decrease (annealing up to 420 ◦ C) fol-
The hardness response to the same isochronal annealing lowed by ∼16% increase over the initial value (annealing
is very weak at temperatures lower than the extrusion tem- up to 540 ◦ C). Partial dissolution of fine Al3 (Sc1−x Zrx ) par-
ticles was also observed in Al–2.7Mg–0.24Sc–0.08Zr and
Al–2.7Mg–0.25Sc–0.08Zr–0.13Cr–0.13Mn alloys after solu-
tion treatment at 585 ◦ C for 15 h and after isochronal annealing
up to temperatures higher than 480 ◦ C [10].

4. Conclusions

Finely dispersed coherent spherical particles of the


Al3 (Sc1−x Zrx ) phase precipitate in grain interiors as well
as at grain (sub-grain) boundaries during extrusion of the
Al–0.5Sc–0.4Zr and Al–2.7Mg–0.14Sc–0.045Zr alloys pre-
pared by powder metallurgy. This ensures high mechanical
properties and their stability up to the extrusion temperature.
Precipitation of Al3 (Sc1−x Zrx ) particles at grain (sub-grain)
Fig. 6. Differential curve of cold rolled (CR) Al–Mg–Sc–Zr fitted by Gaus- boundaries inhibits recrystallisation at least up to ∼500 ◦ C in
sian curves of single annealing stages. Single Gaussian stages represent at: alloys produced by powder metallurgy.
−123 ◦ C annealing of dislocations; −236 ◦ C precipitation of tiny particles; The precipitation of very fine particles of the transient ␤
−305 ◦ C dissolution of tiny particles; −375 ◦ C precipitation of Al3 Mg2 par-
phase (or GP zones) of the Al–Mg system, which increases the
ticles; −434 ◦ C precipitation of Al3 (Sc, Zr) particles; −530 ◦ C dissolution of
Al3 Mg2 and Al3 (Sc, Zr) particles. Differential curves: measured, ; fitted, thick resistivity of the Al–2.7Mg–0.14Sc–0.045Zr alloy, was detected
solid line. by electrical resistivity measurements and TEM observations
374 B. Smola et al. / Materials Science and Engineering A 462 (2007) 370–374

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Acknowledgement [9] S. Lathabai, P.G. Lloyd, Acta Mater. 50 (2002) 4275–4292.
[10] B. Smola, I. Stulı́ková, V. Očenášek, J. Pelcová, Mater. Chart. 51 (2003)
The financial support by the Czech Science Foundation 11–20.
[11] K.U. Kainer, R. Unal, Proceedings of the 1998 Powder Metallurgy World
(Project # 106/04/1353) is gratefully acknowledged.
Congress and Exhibition, Granada, Spain, 1998, pp. 284–288.
[12] T.B. Masalski, Binary Alloy Phase Diagrams, vols. 1–3, 2nd ed., American
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