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IEEE TRANSACTIONS ON MAGNETICS, VOL. 49, NO. 8, AUGUST 2013

Synthesis of Room-Temperature Magnetic Refrigerants Based on La-Fe-Si

by a Novel Process
H. N. Bez , C. S. Teixeira , B. G. F. Eggert , J. A. Lozano , M. S. Capovilla , J. R. Barbosa, Jr. , and
P. A. P. Wendhausen
Mechanical Engineering Department, LabMat, Campus Universitrio Reitor Joo David Ferreira Lima, Florianpolis, Santa
Catarina 88040-900, Brazil
Mechanical Engineering Department, POLO Research Laboratories for Emerging Technologies in Cooling and Thermophysics,
Campus Universitrio Reitor Joo David Ferreira Lima, Florianpolis, Santa Catarina 88040-900, Brazil
In this contribution, aiming to scale-up the production of the material to be used as a magnetic refrigerant, important results are
reported regarding the preparation of La(Fe, Si) compounds by a novel powder metallurgical approach. Additionally, with this new
processing route, near net shape components can be fabricated. Based on the ability of some rare-earth compounds to absorb and
desorb hydrogen in a controllable manner, an La-based alloy, obtained by conventional casting, was used as a precursor material for this
approach. Due to the high content of La-rich phase (LaFeSi), it was possible to decrepitate the ingot into small pieces via interstitial hydrogen insertion. The decrepitated material was further milled, sieved and subsequently pressed into cylinders. A further consolidation
step was carried out by sintering. During sintering, simultaneously, the microstructure was homogenized and the porosity controlled.
After a 6 h heat-treatment at 1423 K, the samples approached single-phase La(Fe, Si) , with a relative phase amount of 99 wt%. The
residual porosity, inherent of powder metallurgy, plays an important role in a final hydrogenation step necessary to tune the transition
temperature. This transition-temperature, around which the magnetocaloric effect is useful for refrigeration, was verified via DSC, while
direct measurements of the adiabatic temperature change,
, were carried out to quantify the magnetocaloric effect.
Index TermsHydrogen-decrepitation-sintering-hydrogenation (HDSH) process, La-Fe-Si alloys, magnetocaloric materials.

I. INTRODUCTION

ECENTLY, magnetic refrigeration based on the magnetocaloric effect (MCE) has become a promising alternative for developing room-temperature cooling technologies [1].
The earliest studies were based in pure Gd and Gd-based alloys.
However, the aim of achieving higher MCE, and consequently
higher device efficiency, led to the development of other alloys
based in transition metals and rare-earth elements [2], [3]. In
addition, in order to apply these materials to magnetic refrigeration, they must be tailored into physical components, which
in turn must fulfill some specific requirements, such as an appropriate shape, mechanical integrity and the desired magnetocaloric properties. Aiming at these properties, some efforts
regarding the possible processes must be taken. To guarantee
that the material is processable, the substance must lay in an
intermediate state before the final desired properties are finally
achieved. This is a common prerequisite when a specific shape
is needed for the targeted component and sometimes taken for
granted by materials engineers. In the case of magnetic refrigerants there is still not a defined special shape, but instead it is
desired that the synthesis of new magnetic refrigerants allows
the fabrication of diverse geometries since the optimization design of AMRs is still in its early stages. There is a continuous
need for new ideas to fulfill this requirement as has been demonstrated by Katter et al., 2010 [4], [5].
In the context of developing suitable materials for magnetic
refrigeration, La-based compounds, which crystallize in the
Manuscript received February 07, 2013; accepted March 20, 2013. Date
of current version July 23, 2013. Corresponding author: H. N. Bez (e-mail:
hnbez@emc.ufsc.br or hnbezz@gmail.com).
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TMAG.2013.2256111

NaZn -type structure, are one of the most promising. In these

compounds, Si plays an important role, since binary LaFe
itself is not stable, as its formation enthalpy is positive [6].
Concerning the establishment of a NaZn -type structure (1:13
phase), a few Fe atoms must be substituted by some other
elements, e.g., Si and Al [3]. The incorporation of Si results
in a shrinkage due to the smaller atomic size compared to Fe
[6]. Literature has shown that NaZn -type structure of LaFe
[7].
Si only stabilizes within a range of
Such alloys are generally produced by conventional induction or arc-melting followed by a moderate cooling-rate casting
process, which leads to a heterogeneous microstructure comSi
-Fe and also La-rich phases
posed of the desired LaFe
[8]. In addition, the as-cast alloys must undergo an annealing
treatment in order to be homogenized and consequently to increase the amount of the desired 1:13 phase [8]. It has been frequently reported that this treatment may last days at high temperatures to achieve almost single 1:13 phase alloys [9].
In favor of reducing this long-time process, other processes
have been used. Melt spinning has been reported to allow the
synthesis of high content of 1:13 phase, and consequently a low
content -Fe remained (about 5 wt%) [10]. Recently, a novel
technique showed an alternative way to produce the desired
phase 1:13, by the reduction-diffusion (R/D) process to synthesize La-Fe-Si compounds [11]. However, all of these processes are used to obtain samples with the desired phase either
in powder, ribbon form or ingots shape. Moreover, these rearound
sulting forms do not fulfill the requirements of both
room-temperature and a specific shape to employ in an AMR
device. In order to use magnetocaloric materials in refrigeraaround room-temperature to optimize
tion, they must have a
the MCE. One way to enhance the
is by introducing some
small atoms interstitially, such as C and H [12]. From this point

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BEZ et al.: SYNTHESIS OF ROOM-TEMPERATURE MAGNETIC REFRIGERANTS BASED ON LA-FE-SI

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sieved to get particles smaller than 25 m to avoid grain texture patterns during the XRD characterization. The density of
the sintered (bulk) samples was measured by the Archimedes
method. Also, a microstructural characterization of the samples was performed by scanning electron microscopy (SEM)
on a Phillips microscope model Phillips30. The Curie temperatures of the samples were measured on a differential scanning
calorimeter (DSC), from TA Instruments model 2010. Direct
measurements of the adiabatic temperature change were performed on a home built
-ometer device [15] working in
a temperature range of 258 K to 348 K and under a magnetic
field change of 0 to 1.75 T supplied by a permanent magnet in
a Halbach array.
III. RESULTS
Fig. 1. Relative phase content evolution due to different sintering times.

to the application of these materials as magnetic refrigerants,

there are some requirements before these substances become a
functional material, with the necessary characteristics to the application. Some efforts have been spent on achieving better mechanical properties and important results have been achieved,
for example the La(Fe, Co, Si) produced also via powder metallurgy [4].
This work aims at using powder metallurgy principles to obtain functional La(Fe, Si) materials by using an alternative
route based in a sintering processing with in situ phase homogenization, followed by a hydrogenation process.
II. EXPERIMENTAL PROCEDURE
An induction melted ingot, with a nominal composition of
La
Fe
Si
, has been decrepitated for 1 h, in a 130 kPa
hydrogen atmosphere at 423 K. This process, known as hydrogen decrepitation (HD), inserts hydrogen interstitially in the
rare-earth rich phase, i.e., LaFeSi (1:1:1 phase), expanding it
and, consequently, shattering the phase and then the ingot [13].
After the HD, the ingot pieces were milled in a commercial planetary mill, model Retsch PM100. The particle size was guaranteed smaller than 100 m through sieving. The generated
powder was pressed into cylinders and heated up to 873 K in
vacuum at 6 10 kPa in order to desorb interstitial H, then
an Ar atmosphere at 90 kPa was created and the samples were
heated to 1423 K to sinter the cylinders. Up to this point the
process can be called hydrogen-decrepitation-sintering (HDS).
After this process, the temperature was reduced to 773 K, and
the atmosphere was changed to H at 140 kPa for 2 h aiming the
insertion of interstitial H (hydrogenation) in the bulk samples.
Subsequently, the samples were slowly cooled to room temperature in the furnace. Therefore, the whole process may be called
hydrogen-decrepitation-sintering-hydrogenation (HDSH).
The phase constitution of the samples was determined by
means of powder X-ray diffraction (XRD) on a Phillips XPert
Plus Diffractometer with Cu
radiation and the quantitative
phase analyses were performed by the Rietveld method, using
GSAS code [14]. The samples were milled into powder and

Phase quantification of the XRD measurements is shown in

Fig. 1, summarizing the relative phase content evolution, for different sintering times at 1423 K. The values of relative phase
content for 0 h represent the results for the powder before sintering, i.e., the as-cast ingot. At the beginning of the process, the
starting material in a powder form contains less than 20 wt% of
1:13 phase and the majority phase is -Fe. As the graph shows,
the relative amount of 1:13 phase increases quickly in the first
three hours of sintering due to an in situ homogenization. However, to reach more than 99 wt%, the sintering time must be doubled. This is an effect caused by the decrease of chemical gradient through the process, as the chemical gradient is a driving
force for diffusion. Using XRD, no La-rich phase was found,
although this phase is normally present as an undesired phase
in La-Fe-Si alloys produced by other methods, such as casting
and homogenization [8].
The optimized sample with 6 h of heat treatment had its microstructure analyzed by images with SEM right after HDS, as
shown in Fig. 2. Analyzing the BSE image, Fig. 2(a), and comparing with that of SE [Fig. 2(b)], there is only the desired phase
1:13. The black regions correspond to pores that occur in this
powder metallurgy process. These pores are present in almost
all parts made by this technique. The porosity usually is a drawback for the mechanical integrity of the parts, but actually in
the case of this particular process, HDSH, it is an advantage.
Firstly, as shown in earlier studies [16], the porosity may relieve the internal stresses while magnetically cycling the parts
as they reduce the internal constraints. Additionally, the pores
in this process are also used as a free path to the hydrogen, so
these atoms are interstitially inserted in the crystal structure, increasing the
to near room temperature. The density of the
samples right after the sintering process is around 83% of the
theoretical density, for all the different sintering times, showing
that even though 3 h of heat treatment is enough for densification, it is not enough for the homogenization.
With nearly 100 wt% of the desired 1:13 phase, there is
still the need to increase the
to near room-temperature
to apply these materials in room-temperature refrigeration
devices. Therefore, the nearly monophasic samples of 6 h of
heat treatment were hydrogenized, as previously described.
Fig. 3 compares the XRD patterns of the same sample before
hydrogenation (blue line) and after hydrogenation (red line).
As the inset in the graph highlights, there is a shift of the whole

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IEEE TRANSACTIONS ON MAGNETICS, VOL. 49, NO. 8, AUGUST 2013

Fig. 4. Image of a crack generated due to the expansion of the 1:13 phase.

Fig. 2. SEM images at the same position with (a) BSE and (b) SE.
Fig. 5. Adiabatic temperature change while magnetization and demagnetization of the hydrogenized sample.

Fig. 3. Comparison of a La(Fe, Si) sample with 6 h of heat treatment before

hydrogenation (blue line), HDS, and after hydrogenation (red line), HDSH, with
an inset highlighting the shift after hydrogenation.

pattern to smaller angles after the hydrogenation process. This

is expected since the interstitial hydrogen modification expands
the crystal structure. The successful hydrogen insertion was

also proved through DSC measurements, not shown here for

conciseness, at which the observed magnetic phase transition
from ferromagnetic to paramagnetic is around 331 K.
After the whole HDSH process was finished for the nearly
monophasic part, the microstructures of the parts were analyzed
by means of SEM. Fig. 4 shows a crack that may be generated
due to the hydrogenation step. The expansion induced by the
interstitial hydrogen causes internal stresses, and as La(Fe,Si)
behaves as a brittle material, cracks are created. Even though
cracks are present, the structural integrity was kept, i.e., the part
was not shattered. One hypothesis to this behavior is even with
the nucleation of a crack, its propagation is stopped due to the
presence of a pore on its way. So the porosity inherent of the
HDSH process, in addition to relieving the internal stresses and
used as a free path for hydrogen insertion, may be also correlated to a prevention for crack propagation and, consequently,
keeping the structural integrity of the parts.
A maximum magnetocaloric temperature change of 2.2 K
was obtained while demagnetizing the hydrogenized sample
around 332 K, as shown in Fig. 5. The direct measurement
results of the MCE were attained for a magnetic field change of

BEZ et al.: SYNTHESIS OF ROOM-TEMPERATURE MAGNETIC REFRIGERANTS BASED ON LA-FE-SI

1.75 T and a demagnetizing factor,

, on the sample of 0.32.
A calculated magnetization curve was determined through the
reversibility constraint described as the literature shows [17].
The difference between the calculated and the experimental
magnetization curve is due to a temperature difference between
the magnets and the sample which allows some heat transfer
that violates the adiabatic conditions in this experiment. The
Halbach array was kept colder than the temperature of the
sample to prevent any demagnetization of the magnets.
IV. CONCLUSION
Aiming at a functional material for magnetic refrigeration,
La(Fe,Si)
bulk samples were prepared via HDSH, a novel
process. The obtained parts presented more than 99 wt% of the
desired 1:13 phase, after only 6 h of heat treatment in a temperature of 1423 K. The
was increased from below room temperature to about 331 K, where a maximum adiabatic temperature
change of 2.2 K was attained. The samples had no considerable geometric change besides the expected shrinkage from sintering. Even though the structural integrity of these parts were
not lost, there must be a further improvement due to the inner
fragility of this material which is aggravated by the hydrogenation. The optimization of the HDSH process and the structural
integrity of LaFe
Si H parts are underway and will be
reported in forthcoming publications.
ACKNOWLEDGMENT
The authors would like to express their gratitude to the
Brazilian agencies CAPES, CNPq and FAPESC for scholarships and financial support for infrastructure funding and to
LCME-UFSC for the access to SEM facilities. The authors
would like to express their gratitude to J. Cardoso de Lima, A.
da Cas Viegas, C. M. Poffo, P. V. Trevizoli and D. P. Alcalde
for the fruitful discussions and measurements of the thermal
and magnetic phenomena.
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