Materials Characterization 58 (2007) 805 – 808

Structural and magnetic properties of mechanically milled

Y1−xPrxCo5 compounds [x = 0, 0.1, 0.3, 0.5]
J.T. Elizalde Galindo a,⁎, H.A. Davies b , J.A. Matutes-Aquino c
a
Department of Physics, University of Texas at El Paso, 500 W. University Avenue, El Paso, TX 79968, USA
b
Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield, S1 3JD, UK
c
Centro de Investigación en Materiales Avanzados, S.C (CIMAV), Miguel de Cervantes 120, Chihuahua, Chih., 31109, México
Received 14 June 2006; received in revised form 18 October 2006; accepted 16 November 2006

Abstract

Samples of composition Y1−xPrxCo5 (x = 0, 0.1, 0.3, 0.5) were arc melted in an argon atmosphere, mechanically milled for
various times and heat treated at about 1073 K for short periods of time, in order to obtain nanocrystalline compounds. The X-ray
diffraction patterns after the heat treatment indicated a single hexagonal 1:5 phase for each composition. The unit cell parameters
varied with Pr content in the Y1−xPrxCo5 series. The crystallite size determined from transmission electron micrographs was about
13 nm. The intrinsic coercivity increased with Pr content; a maximum coercivity of 1.17 MA/m and an enhanced relative
remanence magnetization to maximum magnetization ratio σr/σmax = 0.71 were achieved after heat treatment for the composition
Y0.5Pr0.5Co5. The enhanced magnetic properties suggest strong intergranular exchange coupling in this composition, consistent
with the very fine crystallite size.
© 2006 Elsevier Inc. All rights reserved.

PACS: 74.25.Ha; 75.50.Vv; 73.63.Bd; 75.50.Ww

Keywords: Permanent magnets; Magnetic anisotropy; Nanocrystalline materials; High coercivity materials

1. Introduction which facilitates a high coercivity iHc. This is combined

RECo5 (RE = rare earth) intermetallic compounds are
known to have large uniaxial magnetocrystalline
anisotropy fields HA, relatively high saturation magne-
tizations Ms and high Curie temperatures TC, and have
attracted much attention since their discovery in the late
1960's [1]. Most of the attention on this type of alloy has
been focused on SmCo5 due its exceptionally high HA,
⁎ Corresponding author.
E-mail addresses: jose.elizalde.galindo@gmail.com
(J.T. Elizalde Galindo), h.a.davies@sheffield.ac.uk (H.A. Davies),
jose.matutes@cimav.edu.mx (J.A. Matutes-Aquino).
1044-5803/$ - see front matter © 2006 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2006.11.008
with a relatively high maximum energy product
(BH)max, which is a useful figure of merit for permanent
magnets [2]. SmCo5 has been processed by melt
spinning [3,4], mechanical alloying [5] and mechanical
milling [6]. Other compounds in the RECo5 family,
including PrCo5 and YCo5, also possess good magnetic
properties [7–10]. High coercivities have been obtained
for melt spun and mechanically milled YCo5 [8,9,11]
and for mechanically milled PrCo5 [12] with a nanoscale
grain size, stimulating interest in these materials for
possible permanent magnet applications. This paper,
reports the structure, magnetic properties and micro-
structure of nanocrystalline Y1−xPrxCo5 (x = 0, 0.1, 0.3,
806 J.T. Elizalde Galindo et al. / Materials Characterization 58 (2007) 805–808
Table 1
Annealing parameters used for each amorphous powder composition
Composition Heat treatment
Temperature (K) Time (min)
YCo5 1073 2.5
Y0.9Pr0.1Co5 1073 2.5
Y0.7Pr0.3Co5 1073 1 transmission electron microscope (TEM), where the
Y0.5Pr0.5Co5 1073 1 annealed powders were suspended in ethyl alcohol and
0.5) powders obtained by mechanical milling of arc cast
ingots of the different compositions.
2. Experimental details
Raw materials were used in the form of pieces with
purity of 99.9% for Y (Alfa Aesar), 99.9% for Pr (Alfa
Aesar) and 99.8% for Co (Alfa Aesar). They were
weighed with nominal composition Y1−xPrxCo5 (x = 0,
0.1, 0.3, 0.5) and melted in an arc furnace in an
atmosphere of high purity Ar. The ingots were remelted
3 times to ensure homogeneity. The as-cast alloys were
coarsely pulverized and sieved with a 177 μm pore size
sieve. The powders were mechanically milled in a high
purity Ar atmosphere using a SPEX 8000 ball mill for
periods of time ranging from 15 to 240 min. The as-
milled powders were amorphous and these were
annealed at 1073 K in a high vacuum in closed vycor
ampoules for various times, ranging from 1 to 2.5 min.
Annealing was followed by quenching in water. Table 1
Fig. 1. Powder X-ray diffraction patterns for the nanocrystalline
Y1−xPr xCo5 (x = 0, 0.1, 0.3, 0.5) compounds obtained by 240 min
of mechanical milling and subsequent annealing at 1073 K for
times between 1 and 2.5 min. All peaks correspond with those of
CaCu5 hexagonal structure.
shows the optimum annealing conditions used to obtain
each composition in the nanocrystalline state.
X-ray diffraction (XRD) patterns of as-cast, as-milled
and annealed powders were measured with a Siemens
model D5000 diffractometer using Cu-Kα radiation.
The microstructure was observed with a Philips CM200
the suspension deposited on the grid sample holder
with a micropipette. Hysteresis loops were measured at
room temperature with a maximum applied field of
3.98 MA/m using an Oxford Maglab 9100 vibrating
sample magnetometer (VSM), with the annealed
powders glued with polyethyleneglycol 1500 into the
sample holder. Curie temperatures were measured with a
thermogravimetric analyser (TA Instruments TGA
2950).
3. Results and discussion
Fig. 1 shows the X-ray diffraction patterns for the
nanocrystalline Y1−xPrxCo5 (x = 0, 0.1, 0.3, 0.5) com-
pounds, annealed after 240 min of mechanical milling.
These patterns could be indexed with the CaCu5
hexagonal structure [13] indicating that Pr partially
substitutes for Y in the crystalline structure for each
composition. No evidence of secondary phases was
found. Because of the nanometric crystallite size, all
diffraction peaks were markedly broadened. The differ-
ence in (200) reflection intensities between the first two
compositions (x = 0, 0.1) and the last two compositions in
the series (x = 0.3, 0.5) may be due to the fact that the
annealing time was 2.5 min for the former and 1 min for
the latter. Longer annealing times would tend to decrease
any microstrains present and increase the crystallite size,
which in turn would result in increased diffracted
intensities, particularly for the (200) reflection [14].
Table 2 shows the variations of unit cell parameters, a
and c, and Curie temperature, TC, with Pr content for the
nanocrystalline Y1−xPrxCo5 compounds. The cell para-
meters, a and c, increase with Pr content, because the Pr
atomic radius is larger than the Y atomic radius [15,16].
On the other hand, TC decreases with increasing cell
Table 2
Unit cell parameters and Curie temperatures for nanocrystalline Y1−xPrxCo5
compounds obtained with the parameters shown in Table 1
Composition a (Å) c (Å) TC (K)
YCo5 4.950 ± 0.001 3.973 ± 0.001 930.1 ± 0.5
Y0.9Pr0.1Co5 4.960 ± 0.001 3.973 ± 0.001 925.8 ± 0.5
Y0.7Pr0.3Co5 4.970 ± 0.002 3.974 ± 0.002 913.9 ± 0.5
Y0.5Pr0.5Co5 4.982 ± 0.001 3.976 ± 0.001 908.8 ± 0.5
 J.T. Elizalde Galindo et al. / Materials Characterization 58 (2007) 805–808 807

Fig. 2. Characteristic microstructure observed by TEM in the dark field

mode for the nanocrystalline Y1−xPrxCo5 (x = 0, 0.1, 0.3, 0.5)
compounds obtained by 240 min of mechanical milling and
subsequent annealing at 1073 K for times between 1 and 2.5 min.

parameters, as would be expected from the dependence

of the exchange energy on the cell parameters [17,18].
Fig. 2 shows the microstructure of the YCo5
compound observed by TEM in dark field mode
which is also representative of other compositions of
the Y1−xPrxCo5 system (x = 0, 0.1, 0.3, 0.5). A uniform
microstructure is observed within the individual powder
particle which have crystallite sizes in the range 5–
20 nm. Table 3 gives the mean crystallite size dc
obtained by TEM for all the compositions; dc varied
from 8 to 13 nm. These values are well within the range
required for strong exchange coupling between adjacent
crystallites [19].
Fig. 3 shows the hysteresis loops for nanocrystalline
Y1−xPrxCo5 (x = 0, 0.1, 0.3, 0.5) intermetallic com-
pounds. A strong Pr content dependence of coercivity
is observed, while maximum magnetization values,
σmax, were almost independent of Pr content. The
highest coercivity of 1.17 MA/m, combined with a high
relative remanence magnetization to maximum magne-
tization ratio (σr/σmax) of 0.71, was obtained for the
Y0.5Pr0.5Co5 composition milled for 240 min, annealed
at 1073 K for 1 min and quenched in water. The initial
magnetization curves for all compositions suggest a
pinning type magnetization process [20], in good
Fig. 3. Hysteresis loops for the nanocrystalline Y1−xPrxCo5 (x = 0, 0.1,
Table 3 0.3, 0.5) compounds. A strong Pr content dependence of coercivity is
Mean crystallite sizes for annealed Y1−xPrxCo5 (x = 0, 0.1, 0.3, 0.5) observed, while maximum magnetization values were almost
powders obtained with the parameters shown in Table 1 independent of Pr content.

Composition Crystallite size

(nm) agreement with that reported by Sánchez et al. [21] for
YCo5 13 ± 5 Y0.5Pr0.5Co5. Due to the very fine mean crystallite sizes
Y0.9Pr0.1Co5 11 ± 7 of ∼10 nm for these materials, the inter-crystalline
Y0.7Pr0.3Co5 12 ± 5 exchange coupling penetrates deeply in the nanocrys-
Y0.5Pr0.5Co5 8±3
tallite volume and gives rise to the formation of
808 J.T. Elizalde Galindo et al. / Materials Characterization 58 (2007) 805–808
multicrystalline or interaction domains. The possible
pinning sites must be located at the crystallite bound-
aries. As the magnetization was not saturated, even for
the maximum applied field, then all the hysteresis loops
are minor loops. This is characteristic behavior for these
high anisotropy RECo5 nanocrystalline compounds [22].
A direct relationship between the Pr content and
coercivity was found for the Y1−xPrxCo5 compounds.
The highest coercivity of 1.17 MA/m corresponds to the
Y0.5Pr0.5Co5 compound after 240 min of mechanical
milling and annealing at 1073 K for 1 min. It is
interesting to note that even with the replacement of half
of the Y by the Pr, the coercivity value is greater than one
half of that reported for PrCo5 [12]. On the other hand,
the σr/σmax ratio was more than 0.5 in all cases indicating
an enhancement of the remanence caused by the strong
inter-crystallite exchange coupling. The high iHc and σr/
σmax values (as seen for m Fig. 3) have their origin in the
large anisotropy field of the RECo5 phase and in the very
fine and uniform nanocrystallite dimensions.
4. Conclusions
Improved magnetic properties of the high magneto-
crystalline anisotropy Y1−xPrxCo5 (x = 0, 0.1, 0.3, 0.5)
intermetallic compounds were obtained due to the ultra-
fine and homogeneous nanocrystalline microstructure
developed by the mechanical milling processing. The
Curie temperature of these compounds decreases with
increasing Pr content. The enhanced remanence is
attributed to the strong exchange interactions between
the crystallites having average sizes in the range 8–
13 nm. The highest coercivity of 1.17 MA/m, combined
with a high σr/σmax ratio of 0.71, was obtained for the
Y0.5Pr0.5Co 5 composition milled for 240 min, annealed
at 1073 K for 1 min and quenched in water. In summary,
the present study shows the possibility of improving the
magnetic properties of the nanocrystalline YCo5 inter-
metallic compound by partial substitution of the Y by Pr.
Acknowledgements
This work was carried out at the University of
Sheffield (U.K.) and at CIMAV, S.C. (Mexico), with the
support of the E.U. ALFA Programme contract no:
AML/B7-311/97/0666/I I-0147-FI.
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