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Scripta Materialia 87 (2014) 5–8
www.elsevier.com/locate/scriptamat

Effect of Er additions on the precipitation strengthening

of Al–Hf alloys
H. Wu, S.P. Wen,⇑ K.Y. Gao, H. Huang, W. Wang and Z.R. Nie⇑
School of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, People’s Republic of China
Received 13 January 2014; revised 24 April 2014; accepted 9 June 2014
Available online 18 June 2014

Precipitation strengthening was investigated in dilute Al–Er, Al–Hf and Al–Er–Hf alloys. Combined addition of 0.045 at.% Er
and 0.18 at.% Hf in Al gives a maximum hardness of 640 MPa, which is significantly higher than that of the Al–0.18Hf and Al–
0.045Er alloys. The remarkable strengthening can be attributed to the addition of Er, which accelerates the precipitation kinetics
and stimulates the decomposition of Al–Hf. The effect of Er and Hf on precipitation strengthening in Al–Er–Hf alloys is discussed.
Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Aluminum alloy; Precipitation; Erbium; Hafnium

The group IV transition elements (Ti, Zr, Hf) are
extremely slow diffusers in Al, and thus Al–transition
element systems show particular promise for developing
thermally stable Al-based alloys [1]. Ordered metastable
L12-structured Al3Zr precipitates from supersaturated
Al–Zr solid solution during post-solidification aging;
this precipitate is coherent with the Al matrix and ther-
mally stable at elevated temperature [2,3]. Nevertheless,
the maximum solubility of Zr in Al is only 0.083 at.%
and therefore the volume of precipitates is limited. Hf
shows many similarities to Zr although it is a relatively
rarely used alloying addition. The maximum solubility
of Hf in Al is 0.186 at.%, which is larger than that of
Zr [4]. Metastable cubic L12-structured Al3Hf precipi-
tates first decompose from the supersaturated Al–Hf
solid solution—and then transform to the equilibrium
tetragonal structure after prolonged aging at elevated
temperatures (>400 °C) [5]. However, in Al–1 wt.% Hf
alloy, no obvious homogeneous distribution of precipi-
tates can be observed and the number density of the pre-
cipitates is relatively low, even after thousands of hours
of aging at 450 °C [6]. This indicates that Al3Hf disper-
soids are extremely difficult to precipitate in binary Al–
⇑ Corresponding authors. Tel.: +86 10 67396439; fax: +86 10
67391536 (S.P. Wen); e-mail addresses: wensp@bjut.edu.cn;
zrnie@bjut.edu.cn
Hf alloys due to the low driving force for precipitation
of Al3Hf and the sluggish diffusivity of Hf.
Precipitation hardening and thermal stability can be
further enhanced by the joint addition of Sc and Hf in
Al due to the formation of L12-structured Al3(Sc,Hf)
precipitates [7,8]. Sc and Hf segregate to the dendrite
peripheries and interiors, respectively, which results in
homogeneous distribution of precipitates after aging
[8,9]. There is a eutectic reaction in Al with the addition
of heavy rare-earth (RE) elements Er and Yb, resulting
in a stable L12-structured Al3Er and Al3Yb phase in a-
Al [10], which is similar to that in Al with addition of Sc.
In the last few years, Er and Yb have become relatively
frequently used as alloying elements in Al-alloy to sub-
stitute for the expensive element Sc [11,12]. Further-
more, it has been reported that Er and Yb can induce
precipitation in Al–Zr alloys [13–15]. For instance, a sig-
nificant precipitation strengthening is obtained in Al–
Er–Zr alloys, which can be attributed to the acceleration
of the precipitation kinetics of Al–Zr by a synergistic
effect of Zr and Er [13,15]. If the same synergistic effect
can be achieved in Al–Er–Hf alloy, a precipitation hard-
ening effect may also be obtained. Thus far, however,
the effect of Er and Hf on precipitation strengthening
in Al–Er–Hf has never been reported. In this paper,
the isochronal and isothermal age behavior will be
investigated in Al–Er–Hf to clarify the effect of Er on
the precipitation of Al–Er–Hf alloys.

http://dx.doi.org/10.1016/j.scriptamat.2014.06.005
1359-6462/Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
6 H. Wu et al. / Scripta Materialia 87 (2014) 5–8
Table 1. Compositions of the experimental alloys (at.%).
Samples Nominal Verified
composition composition
Er Hf Er
Al–0.045Er 0.045 — 0.048
Al–0.18Hf — 0.18 — 0.175
Al–0.045Er–0.1Hf 0.045 0.1 0.04
Al–0.045Er–0.18Hf 0.045 0.18 0.044
Four experimental alloys were cast from the commer-
cially pure Al (Fe: 0.04 wt.%; Si:0.03 wt.%), Al–6 wt.%
Er and Al–4 wt.% Hf master alloys. The starting materi-
als were melted in a crucible furnace by heating to
790 °C. After thorough stirring, the melt was poured into
an iron mold to produce a 30  90  150 mm3 plate and
quickly cooled to ambient temperature. The composi-
tions of the alloys are given in Table 1 (all compositions
are in at.% unless otherwise noted), which were verified
by inductively coupled plasma-atomic emission spectros-
copy. The castings were homogenized at 640 °C for 24 h
and then water quenched to ambient temperature. Two
separate aging studies were conducted: (i) isochronal
aging in 3 h steps of 25°Cfor temperatures ranging from
150 to 600 °C; and (ii) isothermal aging at 350 °C for dif-
ferent times ranging from 0.1 to 500 h.
Vickers microhardness measurements were performed
on polished samples using a load of 200 g and a dwell
time of 10 s. At least 10 indentations were made per sam-
ple across several grains. The microstructural evolution
was investigated by transmission electron microscopy
(TEM) using a JEOL 2100 microscope TEM foils were
prepared by twin-jet polishing with an electrolyte solu-
tion of 30% nitric acid and 70% methanol at the voltage
of 15 V DC and the temperature below 25 °C.
Figure 1 displays the precipitation behavior of
Al–0.045Er, Al–0.18Hf, Al–0.045Er–0.1Hf and
Al–0.045Er–0.18Hf during isochronal aging as deter-
mined by microhardness. The hardness of Al–0.045Er
increases between 150 and 250 °C and achieves a peak
of 422 ± 15 MPa at 250 °C, then decreases rapidly at
higher temperature. However, the homogenized Al–
0.18Hf has no strengthening effect, and the microhard-
ness maintains nearly constant over the whole tempera-
ture range. Hallem [16] also reported that the hardness
of Al–0.95 wt.% Hf alloy was fairly constant after aging
Figure 1. Evolution of Vickers microhardness during isochronal aging
for Al–0.045Er, Al–0.18Hf, Al–0.045Er–0.1Hf and Al–0.045Er–0.18Hf
alloys.
in the temperature range between room temperature and
550 °C.
The precipitation hardening behavior of Al–Er–Hf is
Hf distinct from that of Al–Er and Al–Hf. With the addi-
tions of Hf in Al–Er, the rate of strengthening between
—
100 and 250 °C decreases, and the peak hardness is also
0.11
delayed. An analogous delay of the peak hardness was
0.185 reported in Al–Er–Zr [13,17] and Al–Yb–Zr [14] with
increasing amount of Zr. For the Al–0.045Er–0.18Hf
alloy, there is an evident increase in hardness between
250 and 475 °C, and the peak hardness of 609 ±
7 MPa at 475 °C is significantly higher than the peak
hardness of other three alloys. When the temperature
is above 500 °C, the microhardness continuously
decreases as a result of the coarsening and dissolution
of the precipitates.
Figure 2 demonstrates the microhardness variation as
a function of aging time for all the experimental alloys
during isothermal aging at 350 °C. The Al–0.18Hf alloy
does not exhibit precipitation hardening after aging for
500 h. The isochronal and isothermal aging hardening
behaviors indicate that the binary Al–Hf alloy has no
significant precipitation strengthening. In the Al–Hf sys-
tem, the maximum solid solubility of Hf in Al is 0.186
at.% at the peritectic temperature of 662.2 °C [4]. This
solid solubility, however, only diminishes slightly with
decreasing temperature (the solid solubility of Hf is
0.1 at.% at 350 °C [4]). Therefore, the driving force
of the precipitation is low and the precipitation process
is very slow due to low diffusivity, which limits the
potential for precipitation strengthening. Thus, the Al–
0.18Hf alloy exhibits negligible age hardening. Indeed,
most of the reported precipitation hardening in Al–Hf
alloys were produced by non-equilibrium cast supersat-
urated alloys [5,18]. The addition of trace alloying ele-
ments, e.g. Si or Fe, to Al–Hf alloy in order to
increase the driving force and speed up the precipitation
process of Al3Hf has been reported [16,19]. The results
show that the distribution of spherical Al3Hf dispersoids
in Al–1.1 wt.% Hf–0.15 wt.% Si alloy was still heteroge-
neous and there was no evident precipitation hardening.
As shown in Figure 2, there is a maximum hardness
of 392 ± 11 MPa for Al–0.045Er alloy after aging for
10 min; then the hardness decreases rapidly with over-
aging, which is behavior similar to that of Al–0.03 Er
aged at 400 °C [17]. The hardening rate of Al–
0.045Er–0.1Hf is slower and the peak hardness of
Figure 2. Vickers microhardness vs. aging time at 350 °C for Al–
0.045Er, Al–0.18Hf, Al–0.045Er–0.1Hf and Al–0.045Er–0.18Hf alloys.
 H. Wu et al. / Scripta Materialia 87 (2014) 5–8
360 ± 4 MPa is lower than that of the Al–0.045Er alloy.
With prolonged aging, the hardness decreases more
slowly than that of Al–0.045Er; however, Al–0.045Er–
0.18Hf alloy achieves a peak hardness of 640 ± 8 MPa
after aging for 100 h, and exhibits only a slight over-
aging after aging for 500 h. When aged isothermally at
the same temperature of 350 °C, the peak hardness of
Al–0.04Er–0.08Zr is only 560 MPa after aging for
70 h [13], which is much lower than the peak hardness
of the present Al–0.045Er–0.18Hf alloy. For the iso-
chronal aging, the peak hardness of Al–0.045Er–
0.18Hf is 609 MPa, which is also larger than the
isochronal aging peak hardness of 505 MPa for the
Al–0.04Er–0.08Zr alloy [13].
In order to further understand the precipitation
strengthening behavior, the corresponding microstruc-
tures of the two ternary alloys were characterized using
TEM. Very few precipitates are detected in
Al–0.045Er–0.1Hf after isochronal ageing to 350 °C, as
shown in Figure 3a, and the corresponding hardness is
only 350 ± 5 MPa. Figure 3 shows micrographs pf three
various aging stages of Al–0.045Er–0.18Hf: under-aged
(Fig. 3a), peak-aged (Fig. 3c,d) and over-aged (Fig. 3e),
respectively. The fine precipitates are distributed homo-
geneously in Figure 3b. The number density of the
precipitates is much higher than that of Al–0.045Er–
0.1Hf alloy, and these precipitates are coherent with
the Al matrix, as determined from the Ashby–Brown
strain-field contrast. Figure 3c and d are, respectively,
dark-field and bright-field TEM images of Al–0.045Er–
0.18Hf after aging to 475 °C, showing a homogeneous
distribution of spherical precipitates with an average
Figure 3. TEM micrographs during isochronal aging: (a) bright-field
image of Al–0.045Er–0.1Hf aged to 350 °C; (b, d, e) bright-field image
of Al–0.045Er–0.18Hf aged to 400, 475 and 550 °C, respectively; (c)
corresponding dark-field image of Al–0.045Er–0.18Hf aged to 475 °C;
(f) EDS pattern of precipitates of Al–0.045Er–0.18Hf aged to 550 °C.
7
radius of 3.4 ± 0.3 nm. The microhardness increases by
340 MPa from 100 to 475 °C, owing to the precipitation
of the dense, homogeneously distributed spherical
particles.
Figure 3e shows a TEM micrograph of Al–0.045Er–
0.18Hf aged to 550 °C; the average radius of the precip-
itates, 15.5 ± 0.8 nm, is larger and the number density of
the precipitates is less than those aged at 475 °C, indicat-
ing the coarsening of the precipitates, which is consistent
with the corresponding sharp decrease in microhard-
ness. The inset micrograph of the precipitates in Figure
3e exhibits a dark core surrounded by a brighter shell.
The composition of the precipitate detected by energy-
dispersive spectroscopy (EDS) consists of Al, Er and
Hf, as shown in Figure 3f. Characteristic L12 superlat-
tice reflections of the precipitates are visible in the inset
selected-area diffraction (SAD) pattern in Figure 3d and
e. In published studies of Al–Er–Zr [13], Al–Sc–Er–Zr
[20] and Al–Sc–Hf [7] alloys, Er and Sc are found to seg-
regate to the core of the precipitates, while Zr and Hf
segregate to the periphery of the precipitates due to
the difference in diffusion coefficient between Er, Sc
and Zr, Hf. Therefore, the precipitates in the present
Al–Er–Hf should be L12 structured Al3(Hf,Er), with
an Er-rich core and an enveloping Hf-rich shell, but this
hypothesis needs to be verified in further studies.
Figure 4a and b are bright-field and dark-field images
of Al–0.045Er–0.18Hf alloy after isothermal aging at
350 °C for 100 h. The average diameter of the precipi-
tates is 2.3 ± 0.2 nm, and the corresponding microhard-
ness reaches the peak. Figure 4c and d are dark-field and
bright-field micrographs of precipitates after aging for
321 h; these dense dispersed particles have an average
diameter of 3.5 ± 0.4 nm. The average diameter of the
precipitates increases by only 1.2 nm from 100 to
321 h, indicating that the Al3(Hf,Er) precipitates possess
an outstanding resistance to growth and coarsening,
owing to the sluggish diffusibility of the Hf. In addition,
Hf reduces the lattice mismatch between the precipitates
and Al matrix [7,21]. Since the small lattice mismatch
decreases the interfacial free energy of precipitates/
matrix which is the driving force of the coarsening
[22], the addition of Hf retards the growth and coarsen-
ing of Al3(Hf,Er) precipitates.
Combined additions of 0.045Er and 0.18Hf in Al
results in a pronounced strengthening effect compared
with binary Al–0.045Er and Al–0.18Hf alloys. This
results from the formation of coherent L12-ordered
Al3(Hf,Er) precipitates with a structure consisting of an
Er-enriched core surrounded by an Hf-enriched shell.
Similar core–shell structures have been reported exten-
sively in Al–Er-Zr [13], Al–Sc–RE [11,23,24] and Al–
Sc–TM (transition metal) alloys [7,25,26]. By comparing
the precipitation behavior of Al–Er and Al–Er–Hf alloys
in Figures 1 and 2, we can find that the initial precipita-
tion strengthening decreases with increasing Hf concen-
tration, indicating that Hf will retard the precipitation
of Al3Er, and then slow down the initial precipitation
strengthening, as evidenced by the TEM micrographs
in Figure 3a and b. Due to the large supersaturation of
Hf in Al–0.045Er–0.18Hf, the strengthening effect is sig-
nificant. Thus, the isochronal aging peak hardness of Al–
0.045Er–0.18Hf is 100 and 250 MPa larger than the iso-
8 H. Wu et al. / Scripta Materialia 87 (2014) 5–8
Figure 4. Bright-field and dark-field TEM micrographs of Al–0.045Er–
0.18Hf alloy isothermally aged at 350 °C for: (a,b) 100 h; (c,d) 321 h.
chronal aging peak hardness of Al–0.04Er–0.08Zr [13]
and Al–0.06Er–0.06Zr [17], respectively, even if Hf is
seven times more expensive than Zr [27]. Again, although
the precipitation process of Al–Er–Hf alloy is relatively
slow, it shows a strength comparable to that of Al–
0.06Sc–0.02Er [11] and Al–0.1Sc–0.17Hf [16]. Addition-
ally, Er and Hf are much cheaper than Sc, thus substitut-
ing Er and Hf for the costly Sc contributes to reducing
the cost of these alloys.
Base on the above experimental results, we can deduce
that the enhanced strengthening effect of Al–Er–Hf
alloys must be attributed to the synergistic effect of Er
and Hf. On one hand, Hf can retard the decomposition
of Al–Er due to the interaction between Er and Hf and
the enveloping Hf-enriched shell as a barrier can retard
the growth of the precipitates. Moreover, the Hf-
enriched shell can reduce the lattice parameter mismatch
and concomitantly the precipitate–matrix interfacial
energy, which can slow down the coarsening process of
the precipitates. On the other hand, the pre-existing
Al3Er precipitates which form below 400 °C offer more
heterogeneous nucleation sites for the sluggish Hf atoms,
thereby increase the driving force and speeding up the
precipitation of Al3Hf; thus Er accelerates the precipita-
tion and stimulates the decomposition of Al–Hf. There-
fore, the enhanced precipitation-strengthening effect and
excellent thermal stability of Al–0.045Er–0.18Hf can be
explained by the synergistic effect of Er and Hf.
In summary, the precipitation strengthening of
Al–Er, Al–Hf and Al–Er–Hf alloys was investigated
Al–0.045Er achieves a peak hardness of 422 MPa. Al–
0.18Hf exhibits no age hardening due to the low driving
force and slow precipitation process of Al3Hf.
Al–0.045Er–0.18Hf alloy achieves a maximum hardness
of 640 MPa, which is significantly higher than that of
Al–0.045Er and Al–0.18Hf alloys due to the dense
homogeneously distributed L12-structured Al3(Hf,Er)
nanoprecipitates. The synergistic effect of Er and Hf
can explain the enhanced precipitation hardness and
excellent thermal stability of Al–0.045Er–0.18Hf. Er
accelerates the precipitation process and stimulates the
decomposition of Al–Hf, while Hf retards the decompo-
sition of Al–Er and slows down the growth and
coarsening of the precipitates.
The work is supported in part by the National
Key Basic Research & Development Plan Project (No.
2012CB619503), National Natural Science Foundation
Project (Nos. 51201003 and 51101001), the National
High Technology Research and Development Program
(No. 2013AA031301), the International Science & Tech-
nology Cooperation Program of China (2013DFB
c50170), and the Beijing Municipal Science Foundation
of Education Commission (KM201310005002).
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