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Scripta Materialia 95 (2015) 5053
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A new type of La(Fe,Si)13-based magnetocaloric composite with amorphous

metallic matrix
Maria Krautz,a Alexander Funk,a Konstantin P. Skokov,b Tino Gottschall,b Jurgen Eckert,a,c Oliver

Guteischb and Anja Waskea,
a
IFW Dresden, Institute for Complex Materials, PO Box 270116, D-01171 Dresden, Germany
b
TU Darmstadt, Materials Science, Alarich-Weiss-Str. 16, D-64287 Darmstadt, Germany
c
TU Dresden, Institute of Materials Science, Helmholtzstr. 7, D-01069 Dresden, Germany
Received 4 September 2014; revised 1 October 2014; accepted 3 October 2014
Available online 18 October 2014

We report on novel magnetocaloric composites based on La(Fe,Si)13 particles in an amorphous metallic matrix. Hot compaction at the glass
transition temperature, Tg, of the matrix prevents crack formation as commonly occurs in conventional hot-compacted La(Fe,Si)13 material. This
damage can aect the magnetocaloric performance. The approach in the present paper shows that the La(Fe,Si)13 particles stay intact due to the
buer-eect of the amorphous and ductile matrix at Tg. Therefore, the magnetocaloric properties of the composites are almost independent of
the compaction pressures.
2014 Published by Elsevier Ltd. on behalf of Acta Materialia Inc.

Keywords: Metal matrix composites; Hot pressing; Three-dimensional tomography; Magnetocaloric eect

The increasing demand for saving resources has
triggered intense research activities into energy ecient
technologies. Magnetic refrigeration, based on the magnet-
ocaloric eect exhibited by a number of solids, could
replace conventional compression-based cooling in certain
applications. Up to now, the focus of solid refrigerants
has been on intermetallic compounds with a rst-order
phase transition. Such materials, e.g. La(Fe,Si)13 [1,2],
Mn-based alloys with Fe2P-structure [3] or Gd5Si2Ge2 [4],
undergo a eld-induced coupled magnetostructural transi-
tion, which is the origin of a giant magnetocaloric eect
(MCE). In La(Fe,Si)13 the volume change during the tran-
sition can exceed 1%, depending on the Si content [5]. This
magnetovolume eect and the low mechanical ductility of
La(Fe,Si)13 cause facile crack formation and propagation
through the magnetocaloric body after several eld cycles
and the degeneration of the microstructural integrity.
It has been found that mechanical stability can be
enhanced in hot compacted La(Fe,Si)13 powder involving
a certain amount of pores [6]. However, due to the forma-
tion of a-Fe as secondary phase at higher compaction tem-
peratures, the observed adiabatic temperature change,
DTad, is reduced. Further, the pores, being poor thermal
conductors, have a negative impact on the magnetocaloric
performance since they reduce thermal contact between
the La(Fe,Si)13 particles.
Corresponding author; e-mail: a.waske@ifw-dresden.de
Porosity can be reduced to some extent by using a bimo-
dal distribution of the particle size. However, increasing the
fraction of small particles lling up the space between lar-
ger particles is unfavorable with respect to the magnetoca-
loric properties of such particle ensembles as the MCE
decreases with particle size [7,8]. This behavior is generally
explained by the collective transition of the particles which
becomes less pronounced when the particle size is reduced.
In bulk material, grains are constrained and the magne-
tovolume transition of one grain causes the neighboring
grains to transform immediately. In porous samples, the
contact between neighboring grains is less pronounced,
the constraints are reduced and each grain transforms indi-
vidually. The transition width compared to bulk material is
therefore larger in porous particle ensembles and the MCE
is decreased.
Hence, an ideal composite would consist of large parti-
cles with a single particle size which are compacted at low
pressure to prevent cracking (thus preventing the reduction
of the particle size) and using a ductile matrix material as a
binder to decrease the amount of pores. Polymer-bonded
La(Fe,Si)13 composites have been proposed, in order to
increase the processability into optimized shapes [911].
The impact of the matrix material, e.g. a polymer with
low thermal conductivity, on the overall adiabatic temper-
ature change is still under discussion.
In the present paper, we compacted La(Fe,Si)13 particles
together with an amorphous Pd40Cu30Ni10P20 (at.%) matrix

http://dx.doi.org/10.1016/j.scriptamat.2014.10.002
1359-6462/ 2014 Published by Elsevier Ltd. on behalf of Acta Materialia Inc.
 M. Krautz et al. / Scripta Materialia 95 (2015) 5053
material at its glass transition temperature Tg. At Tg, the
amorphous metallic alloy (metallic glass) becomes soft.
During the compaction process the matrix which can now
be deformed will ow through the La(Fe,Si)13 pellet and ll
the porous space similar to liquid-phase sintering. To prove
this concept, a Pd-based material was chosen as the amor-
phous matrix; however, the compaction process can be
applied to any amorphous metallic alloy with good glass
formability. The principle of compaction is illustrated in
Figure 1.
The magnetocaloric component with nominal composi-
tion LaFe11.6Si1.4 was prepared by arc melting and subse-
quent annealing for 7 days at Tann = 1323 K to obtain an
almost single-phase microstructure. From X-ray diraction
(XRD) measurements (not shown), La(Fe,Si)13 was found
to be the majority phase; a-Fe can be considered the sec-
ondary phase with an amount of 10 wt.%. For compac-
tion, La(Fe,Si)13 particles with a size distribution of
d = 160250 lm were used which are in the suggested range
for good magnetocaloric performance [10]. The amorphous
alloy Pd40Cu30Ni10P20 (at.%) is well known for its excellent
glass formability [12] and has been prepared by Cu-mold
casting as described elsewhere [13] and powderized to par-
ticle sizes d < 60 lm in a Retsch mill MM 301.
As the glass transition temperature was determined by
dierential scanning calorimetry (heating rate 10 K min 1)
to be Tg = 569 K, the composites were heated up to
Tp = 570 K in the mold at a rate of Tp = 20 K min 1. Such
a low compaction temperature is advantageous, since the
formation of secondary a-Fe can be minimized. At the peak
temperature pressures of p = 320, 640 and 890 MPa, respec-
tively, were applied for t = 10 min. Pressures <1 GPa were
chosen since severe damage occurs at pressures p > 1 GPa
according to Ref. [10]. La(Fe,Si)13 particles without amor-
phous alloy addition were compacted as reference samples.
A minimum pressure of p = 445 MPa was required to
ensure mechanical integrity of the pure sample. Therefore,
two pure reference samples mirroring the inuence of the
Figure 1. Hot compaction of a La(Fe,Si)13-based composite at Tg of
the amorphous component.
51
upper and lower pressure limit have been compacted at
p = 445 MPa and 890 MPa. After hot compaction, XRD
measurements on the composites were performed with a
Philips XPert Plus Diractometer with Co Ka radiation to
exclude crystallization of the matrix after compaction. Iso-
thermal magnetic measurements of all samples (M vs. l0H
from 0 to 2 T) in the vicinity of the transition temperature
Tt of the LaFe11.6Si1.4 component were performed in a
Quantum Design SQUID and the entropy change DSiso
was calculated from these curves via the Maxwell relation.
Further, direct measurements of DTad were performed upon
an applied eld change of Dl0H = 01.95 T [14].
Since the magnetocaloric properties strongly depend on
both the particle size and the amount of magnetocaloric
active material in the composites [10], it is necessary to dis-
cuss the impact of the compaction pressure on the degree of
damage and porosity in the pure compacted samples as well
as the composites. X-ray computed tomography (XCT)
provides an insight into the 3-D constitution of the samples
and is a valuable non-destructive tool to capture the above-
mentioned microstructural features. 3-D scans of all sam-
ples were performed with W-radiation using a GE Nano-
tom M device with acceleration voltage U = 100130 kV
and a current I = 100120 lA depending on the sample.
With these parameters a resolution of 2 lm was obtained.
Figure 2 shows slices of the tomographs of pure
La(Fe,Si)13 particles (Fig. 2a,b) and the composites with
amorphous matrix (Fig. 2c,d) compacted at dierent pres-
sures. It can be clearly seen that the pores of the pure com-
pacted samples are replaced by the amorphous matrix to a
large extent. Further, the particles compacted at the highest
pressure p = 890 MPa are less fractured for the composite
than for the pure sample. A greyscale analysis of the 3-D
reconstruction of the XCT slices of each sample shows that
the porosity is reduced with increasing pressure for both the
pure material and the composites (Fig. 2c). During hot
compaction the brittle La(Fe,Si)13 particles with a mean
equivalent diameter of dm = 200 lm break apart. Therefore
an increased number of smaller, fractured particles is pres-
ent in the pure samples with increasing pressure. These
smaller particles tend to accumulate in the space between
larger particles and, hence, the porosity is reduced in sam-
ples compacted with higher pressure.
However, the porosity of the composites is smaller than
that of the pure samples. This reduction is not due to the
rearrangement of fractured particles but to the occupation
of cavities between the La(Fe,Si)13 particles by the amor-
phous component. The mechanical stress applied during
compaction is buered by the deformable, glassy matrix.
As a result the La(Fe,Si)13 particles mostly stay intact
and after compaction a more dense composite is achieved
even at lower pressures.
The inuence of the degree of damage on the magnetoc-
aloric properties in the pure compacted samples is shown in
Figure 3a. It can be conrmed that an increased fragmenta-
tion of the particles leads to a reduction in the maximum
MCE. In comparison to the maximum value for the bulk
sample, the entropy change DSiso decreases drastically by
20% for the sample compacted at 445 MPa and decreases
further for a compaction pressure of 890 MPa. Here, the
amount of small, fractured particles rises with increasing
compaction pressure since the stress buer-eect of the
amorphous component cannot occur. It should be men-
tioned that demagnetization in porous materials might lead
to a decrease in the internal magnetic eld. An estimate of
52 M. Krautz et al. / Scripta Materialia 95 (2015) 5053

Figure 3. Magnetocaloric properties DSiso and DTad as a function of

temperature for the pure samples (a) and composites with 25 wt.%
Pd-based matrix (b) compacted at dierent pressures.

Figure 2. Tomographic slices of pure LaFe11.6Si1.4 (a, b) and the

composite samples (c, d) compacted at dierent pressures. Pores and
cracks appear black, the La(Fe,Si)13 phase appears in grey. White
areas correspond to the Pd-based amorphous phase. (e) Dependence of
the porosity on the compaction pressure for the pure samples (black
squares) and composites (blue circles). The amount of magnetocaloric
La(Fe,Si)13 is indicated. (For interpretation of the references to colour
in this gure legend, the reader is referred to the web version of this
article.)

the demagnetization factors according to Bjork et al. [15] of

the bulk and porous samples did not lead to a signicant
change in the magnetic eld experienced by each sample.
Therefore, we consider the increasing degree of damage
of the particles to be the dominant mechanism for the
reduction of DSiso.
In contrast, the buer-eect of the matrix in the compos-
ites leads to less fractured particles, and therefore the max-
imum of both the entropy change and the adiabatic Figure 4. (a) Evolution of the specic entropy change DSiso with
temperature change is less sensitive to compaction pressure increasing compaction pressure for pure compacted LaFe11.6Si1.4 and
than for the pure samples as shown in Figure 3b. Due to the composites with amorphous component. (b) Volumetric entropy
decreased total amount of La(Fe,Si)13 phase (indicated in change as a function of magnetocaloric phase fraction.
Fig. 2e) the maximum value of DSiso in the composites,
however, is reduced in comparison to the pure compacted
samples. It should be noted that the maximum DTad composites compacted with an amorphous matrix at its
remains of the order of value found in the pure compacted Tg. This conrms the results obtained by XCT. The Pd-
samples, since DTad is an intensive property and indepen- based amorphous matrix buers the mechanical stress dur-
dent of the substance volume. ing compaction, resulting in an almost pressure-, i.e. dam-
The relation between compaction pressure (which is age-, independent entropy change.
directly linked to a certain degree of damage in the samples) The specic magnetic entropy change shown in Figures
and maximum entropy change is summarized in Figure 4a. 3 and 4a is useful in order to compare the results obtained
The decline in the entropy change with increasing compac- in the literature. The majority of articles report the mass-
tion pressure is larger in the pure samples than in the specic magnetic entropy change, since the sample mass
 M. Krautz et al. / Scripta Materialia 95 (2015) 5053
is easy to assess by experiment. However, this specic value
does not reect completely the utility of magnetocaloric
materials, especially for composites and porous (e.g. sin-
tered) materials. According to Russek et al. the magnetic
eld volume (provided by permanent magnets) determines
the price of the refrigerator as a whole. This volume is
the key parameter to be optimized. Therefore, DSiso should
be volumetric rather than based on mass [16]. Moreover,
the specic entropy change in Figure 3 only represents
the inuence of the ratio between the Pd-based matrix
and the La(Fe,Si)13 phase. Pores and cracks are not
included, but nonetheless have large impact, since they
act as dead volume and additionally decrease the con-
straints between the grains (due to fragmentation), which
reduces DSiso further.
Figure 4b shows the volumetric entropy change as a
function of magnetocaloric phase fraction. This gure
enables the inuence on the entropy change of (i) porosity
(which is not considered for specic DSiso), (ii) amount of
magnetocaloric phase and (iii) fragmentation to be distin-
guished, particularly in the pure compacted samples. Inter-
estingly, the pure sample compacted at low pressure,
p = 445 MPa, is in the line with the value of the bulk sam-
ple. This indicates that the fragmentation of particles up to
pressures of p = 445 MPa is not sucient to reduce DSiso
drastically. However the compaction pressure appears to
be too low to ensure mechanical cohesion of the sample
for long-term application.
In contrast, the pure compacted sample at p = 890 MPa
shows the lowest entropy change among the pure samples,
although the active volume is higher than in all other com-
pacted samples: a potential sample with 100 vol.%
La(Fe,Si)13 phase compacted at p = 890 MPa would show
an entropy change of 114 kJ m3 K1 in comparison to
148 kJ m3 K1 of the bulk sample. This leads to the conclu-
sion that it is the increase of the fraction of fragmented
small particles, rather than porosity, that causes the reduc-
tion in DSiso.
In the composites the volumetric DSiso is decreased
because of the smaller amount of magnetocaloric
La(Fe,Si)13 phase. It can be seen that the composite com-
pacted at p = 890 MPa lies on the same line of the pure
sample compacted at the same pressure. Apparently, the
glassy matrix cannot buer suciently the mechanical
stress applied at such large pressure, which is mirrored by
the appearance of numerous cracks inside larger particles
in this composite (recall Fig. 2b, d). On the other hand,
the number of cracks is reduced in the composites com-
pacted at the lower pressures p = 320 MPa and 640 MPa,
which explains why the DSiso values are between those of
the stretched area of bulk and p = 890 MPa. This indicates
that composites can be compacted at medium pressures
(p = 640 MPa) without degradation of the entropy change
by fragmentation. Decreasing the amount of amorphous
metallic matrix could shift DSiso to higher values, close to
that of bulk La(Fe,Si)13.
To summarize, we have clearly demonstrated the bene-
cial buer-eect on brittle LaFe11.6Si1.4 particles when com-
pacted together with a ductile amorphous metallic alloy at
its glass transition temperature. The degradation of the
53
magnetocaloric properties by compaction at higher pres-
sure is reduced in comparison to that of compacted pure
LaFe11.6Si1.4 particles.
Moreover, by means of the deformable amorphous com-
ponent, the porosity can be reduced in the composites, since
the LaFe11.6Si1.4 particles are immersed completely. This
has a positive eect on both the mechanical cohesion and
the adiabatic temperature change, which is in the range of
that of the pure compacted samples.
Overall, this work shows a promising route for the pro-
duction of compact refrigerant bodies that can be easily
extended to other brittle giant magnetocaloric materials
whose performance depends strongly on particle size. We
suggest varying the amorphous alloy to achieve dierent
magnetic properties, in order to improve the magnetocalo-
ric eect, as has recently been proposed in other publica-
tions [17,18].
The nancial support of this joint publication by the
German Research Foundation (DFG-Deutsche Forschungsgeme-
inschaft) within the priority program SPP 1599 is gratefully
acknowledged. The authors are thankful to Norbert Mattern for
providing the Pd-based amorphous material.
[1] A. Fujita, Y. Akamatsu, K. Fukamichi, J. Appl. Phys. 85
(1999) 4756.
[2] F.-X. Hu, B.-G. Shen, J.-R. Sun, X.-X. Zhang, Chin. Phys. 9
(2000) 550.
[3] O. Tegus, E. Bruck, K.H.J. Buschow, F.R. de Boer, Nature
415 (2002) 150.
[4] V.K. Pecharsky, K.A. Gschneidner Jr., Phys. Rev. Lett. 78
(1997) 4494.
[5] L. Jia, J.-R. Sun, F.W. Wang, T.Y. Zhao, H.W. Zhang, B.-
G. Shen, D.X. Li, S. Nimori, Y. Ren, Q.S. Zeng, Appl. Phys.
Lett. 92 (4) (2008) 101904.
[6] J. Lyubina, R. Schafer, N. Martin, L. Schultz, O. Guteisch,
Adv. Mater. 22 (2010) 3735.
[7] F.-X. Hu, L. Chen, J. Wang, L.F. Bao, J.-R. Sun, B.-G.
Shen, Appl. Phys. Lett. 100 (2012) 072403.
[8] J. Liu, J.D. Moore, K.P. Skokov, M. Krautz, K. Lowe, A.
Barcza, M. Katter, O. Guteisch, Scr. Mater. 67 (2012) 584.
[9] H. Zhang, Y. Sun, E. Niu, F. Hu, J. Sun, B. Shen, Appl.
Phys. Lett. 104 (2014) 062407.
[10] K.P. Skokov, D.Y. Karpenkov, M.D. Kuzmin, I.A. Radulov,
T. Gottschall, B. Kaeswurm, M. Fries, O. Guteisch, J.
Appl. Phys. 115 (2014) 17A941.
[11] B. Pulko, J. Magn. Magn. Mater. accepted (2014).
[12] L.F. Kiss, T. Kemeny, L. Bujdoso, I. Bakonyi, S. Baskoutas,
P. Poulopoulos, V. Kapaklis, C. Politis, J. Phys. Condens.
Matter 20 (2008) 015211.
[13] N. Mattern, M. Stoica, G. Vaughan, J. Eckert, Acta Mater.
60 (2012) 517.
[14] J. Liu, T. Gottschall, K.P. Skokov, J.D. Moore, O. Gut-
eisch, Nat. Mater. 11 (2012) 620.
[15] R. Bjork, C. Bahl, Appl. Phys. Lett. 103 (2013) 102403.
[16] S.L. Russek, C.B. Zimm, Int. J. Refrig. 29 (2006) 1366.
[17] S.C. Paticopoulos, R. Caballero-Flores, V. Franco, J.S.
Blazquez, A. Conde, K.E. Knipling, M.A. Willard, Solid
State Commun. 152 (2012) 1590.
[18] L.H. Lewis, M.H. Yu, R.J. Gambino, Appl. Phys. Lett. 83
(2003) 515.