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Scripta Materialia 67 (2012) 594–599

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Viewpoint Paper

Magnetic refrigerants with continuous phase transitions:

Amorphous and nanostructured materials
V. Franco⇑ and A. Conde
Dpto. Fı́sica de la Materia Condensada, ICMSE-CSIC, Universidad de Sevilla, P.O. Box 1065, 41080 Sevilla, Spain

Available online 9 May 2012

Abstract—An overview of the magnetocaloric properties of amorphous and nanostructured materials which undergo second-order
phase transitions is presented, paying special attention to open problems which need to be solved to enhance the applicability of
these materials for magnetic refrigeration. The potential of composites is also highlighted, as well as the current status of modeling
these particular subset of magnetocaloric materials.
Ó 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Magnetocaloric effect; Magnetic refrigeration; Amorphous materials; Nanocrystalline materials

1. Introduction materials exhibit a broader DS M peak of a smaller magni-

Magnetic refrigeration is the most straightforward
application of the magnetocaloric effect (MCE). Its great-
er energy efficiency, when compared to refrigeration
based on the compression/expansion of gases, and the
environmental friendliness associated with the lack of
ozone-depleting or greenhouse-effect-related gases, have
attracted considerable attention in recent years. Magnetic
refrigerants need to exhibit an abrupt change in magneti-
zation around room temperature as a consequence of
phase transition. Therefore, the most straightforward
classification of magnetocaloric materials (MCMs) is
according to the order of the phase transition that they
undergo: either second-order (continuous) phase transi-
tions (SOPT), like Gd, or first-order magneto-structural
phase transition (FOPT), like the giant magnetocaloric
material Gd5Si2Ge2 [1]. There are two important param-
eters (in addition to the adiabatic temperature change)
which characterize the magnetocaloric effect: the mag-
netic entropy change, DS M , and the refrigerant capacity,
RC, which is a measure of the amount of heat which
can be transferred between the hot and cold reservoirs.
While FOPT exhibits a large (usually giant) DS M , it is usu-
ally extended over a narrow temperature range, which
diminishes RC. These transitions also imply hysteretic
losses and a slow time response, which would be detri-
mental for refrigerator design, although there are at-
tempts to minimize these effects [2]. In contrast, SOPT
⇑ Corresponding author. E-mail: vfranco@us.es
tude, but the width of the peak keeps RC comparable to
or larger than that of FOPT materials. Moreover, SOPTs
have no thermal hysteresis and, in cases like soft magnetic
amorphous alloys, magnetic hysteresis can also be negli-
gible; the material does not break due to cycling the mag-
netic field (which might happen in the case of
magnetostructural phase transitions due to the different
volume of the phases before and after the transition)
and the electrical resistivity is larger than for crystalline
materials, which diminishes any eddy current losses [3].
An alternative, though more artificial, classification of
magnetocaloric materials is according to their composi-
tion: either rare earth (RE) containing or RE free. The
motivation of this classification is the high cost of RE
and their strategic nature. Therefore, as in many other
fields of magnetism, there are strong trends nowadays
to find alternatives to avoid the use of RE. In fact, the
ideal magnetocaloric material would be one which exhib-
its a giant magnetocaloric effect like in FOPT but without
the thermal hysteresis associated with it, has an DS M peak
that is extended over a large temperature range to enlarge
RC, and has no magnetic hysteresis, strong resistivity,
good thermal conductivity (to exchange heat easily with
the heat transfer medium), good mechanical properties
to ensure integrity of the materials while cycling, excellent
corrosion resistance, and abundant and cheap non-toxic
constituent elements. At the moment, there is no single
magnetocaloricmaterial that fulfills all these require-
ments simultaneously, so designers have to reach a
trade-off between all of them, in combination with the

1359-6462/$ - see front matter Ó 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.scriptamat.2012.05.004
 V. Franco, A. Conde / Scripta Materialia 67 (2012) 594–599
refrigerator design. In fact, refrigerator prototypes are
usually constructed initially with Gd as the refrigerant,
and are modified at later stages to use FOPT materials
as an alternative.
Other manuscripts in this viewpoint set have focused
their attention on FOPT materials, which is probably
the main focus of current magnetocaloric materials
research. In this article we focus our attention on less
conventional refrigerants, like amorphous alloys, nano-
structured materials and composites. They possess some
of the required characteristics mentioned above, while
others still have to be improved. However, research on
this kind of material can help us to gain a deeper
understanding of the magnetocaloric effect and inti-
mately related phenomena such as phase transitions.
There are still open issues in the explanation of the behav-
ior of these materials, which are highlighted herein.
2. Amorphous materials
Amorphous alloys are not the most popular magnet-
ocaloric materials, because they exhibit a small value of
DS pk
M when compared to the giant MCMs (and also with
respect to other SOPT materials). However, the compar-
ison is more favorable when RC is taken into account [3–
5], and this has fostered research on this kind of MCM.
From the application point of view, there are additional
characteristics of transition metal-based amorphous al-
loys which are desirable for magnetic refrigerants, includ-
ing very low cost, higher electrical resistivity than
crystalline materials, high corrosion resistance, tunability
of the Curie temperature (TC) by alloying, good mechan-
ical properties and negligible hysteresis. From a funda-
mental science point of view, the negligible magnetic
anisotropy in these alloys simplifies the study of the mag-
netic transition, making them a good testing ground to
analyze the physics behind the MCE and to develop ther-
modynamic models for representing their response.
The study of the magnetocaloric effect in amorphous al-
loys started back in the 1980s, with the pioneering work
done by Maeda et al. [6], analyzing the influence of alloying
different metallic elements to the (FeM)90Zr10 alloy series.
Belova and Stolyarov continued the studies of transition
metal-based amorphous alloys of the FeCoSiB type [7].
Shortly after those works, the focus changed to RE-based
magnetocaloric materials. RE-based amorphous alloys
have Curie temperatures well below room temperature [8]
and, due to the large magnetic moment of the RE (usually
Gd), exhibit a very large change in magnetic entropy [9].
Transition metal-based amorphous alloys present more
modest values, but the transition temperatures can be easily
tuned to be close to room temperature or above. At the
same time, the cost is usually lower, and they also avoid
the inconveniences of corrosion associated with RE. As a
reference, up to now, the largest RCFWHM (RC calculated
as the product of the DS M peak times the full width at half
maximum) achieved for a transition metal-based amor-
phous alloy for a field of 1.5 T corresponds to 166 J kg1
for Fe88Zr7B4Cu1 and Fe82.5Co2.75Ni2.75Zr7B4Cu1, with
Curie temperatures of 295 and 398 K, respectively [3].
Meanwhile, the alloy with the greatest magnetic entropy
change is Fe80Zr10B10, with 1.99 J kg1 K1 for 1.5 T
[10]. RE-based amorphous alloys have their applicability
595
at temperatures in the 50–200 K range [9], depending on
the alloying elements. Amorphization enhances the corro-
sion resistance of the material and the addition of other ele-
ments, usually cheaper than the rare earths, decreases the
total cost of the materials [11]. Both factors enhance the
applicability of the alloys. Typical values are
1
DS pk
M  3:9 J kg K1 and RC  150 J kg1 for 1.5 T [9].
It is worth mentioning that the largest magnetocaloric re-
sponse in transition metal-based amorphous alloys is
achieved with alloys of the FeZrB type with different addi-
tions of other alloying elements; replacing Zr by other
refractory element decreases the magnetocaloric response
of the alloys. Also, alloying elements which enhance RC
have a deleterious influence on DS pk M . Therefore, a balance
between the two parameters must be found.
One characteristic feature of transition metal-based
amorphous alloys which is the opposite of that of crys-
talline materials and RE-based amorphous alloys is an
increase in magnetic entropy change with increasing
TC of the alloy (Fig. 1). This phenomenological observa-
tion has not been explained yet, but it is a promising fea-
ture for applications of magnetocaloric materials in
thermomagnetic energy-harvesting technologies. The
explanation of this phenomenon can enhance the appli-
cability of other thermomagnetic materials.
In the literature, there is evidence of a linear correla-
tion between the magnetic entropy change peak and the
average magnetic moment of the alloys [12–15]. There-
fore, a strategy to optimize DS pk M would be to increase
the magnetic moment of the alloy without modifying
the position of the Curie temperature too much, as this
must remain close to room temperature. However, we
will see in the following sections that this linear relation-
ship does not emerge from the current theoretical models
used for predicting MCE (Section 5). As a consequence, it
is expected that the study of broader compositional series
of the same base alloy will give rise to breakdowns in the
phenomenologically found linear correlation and will al-
low us to broaden our understanding of the phenomenon.
Most of the magnetocaloric measurements on amor-
phous ribbons are made by indirect magnetization
measurements. The reason for this is that direct measure-
ments of the adiabatic temperature change (DT ad ) require
a thermal mass of the sample which is larger than the mass
of the addenda (sample holder, temperature sensor, etc.).
Further, although there have been recent attempts to ob-
tain the value of DT ad of ribbons by combining numerous
Figure 1. Dependence of the magnetic entropy change of transition
metal-based amorphous alloys on the Curie temperature of the
material. The line is a guide to the eye. The alloy composition of
individual datapoints can be found in Ref. [59].
596 V. Franco, A. Conde / Scripta Materialia 67 (2012) 594–599
pieces of sample, the measurement protocol requires cal-
ibration with ribbons of a magnetocaloric material with a
similar transition temperature [16]. Therefore, the devel-
opment of measurement devices to characterize the mag-
netocaloric response of these low mass samples is a
requirement for further advances in this field. We expect
the appearance, in the near future, of experimental devices
which allow for this kind of characterization.
3. Multiphase materials and composites
There are two main strategies for the optimization of
MCMs: (i) the design of new alloys and compounds with
enhanced performance; and (ii) the use of materials engi-
neering techniques for the optimization of already exist-
ing materials.
In the first strategy, one goal is to increase the mag-
netic moment, which, provided that the characteristics
of the phase transition are maintained, will cause a lar-
ger magnetocaloric response. However, this has to be
done without displacing TC far from room temperature,
which limits the strategies which can be used to achieve
the desired result. This is a highly desirable line of re-
search but with limited expectations of success. At the
same time, cost reduction is a necessity, as is limiting
the use of elements which are extracted from only few
places in the world, because the unavailability of these
strategic materials if the geopolitical situation changes
could endanger the ultimate success of this technology.
This leads to a trade-off between performance and cost.
The materials engineering approach is a complemen-
tary line of research with greater likelihood of success.
The use of known materials as building blocks for devel-
oping composites, nanostructures, graded materials, etc.
is already giving promising results. One of the reasons
for that success is the deep knowledge of the constituent
phases that has been already achieved.
It was pointed out by Smaı̈li and Chahine [17] that the
ideal material for Ericsson-type magnetic refrigerators
should exhibit a constant value of DS M in the temperature
range of the operation of the thermodynamic cycle
(known as table-like MCE). This can be achieved either
by mixing different phases [17–21] or by combining differ-
ent magnetic phase transitions in the same material [22].
Another property which can be optimized by combin-
ing different magnetic phases is RC, as the combination
can make the peak broader (at the expense of decreasing
the magnitude of the peak). Modeling of the magnetoca-
loric response of biphasic materials has shown that RC
can be enhanced by 90% with respect to the initial pure
phases if the appropriate selection of the Curie tempera-
tures of the phases and the fractions of the constituents
is made [20]. It has been shown that in a biphasic system
the majority phase should be that with the largest TC,
and that the addition of minority phases with a TC much
larger than the main phase can decrease the RC of the
composite to a large extent with respect to that of the main
phase. These results from numerical calculations have re-
cently been confirmed by experimental measurements on a
layered composite [19]. Nevertheless, there is still room for
improvement of RC following this strategy, as the whole
parameter space has not yet been covered.
It is worth mentioning that the optimization of the
shape of the peak (to obtain a table-like MCE and to
broaden the peak to enhance RC) should be done specif-
ically for the magnetic field which will be applied in the
refrigerator device, because the optimal fraction of
phases changes with the field.
4. Nanostructured materials
A typical application of magnetic refrigeration is the
domestic or industrial fridge. For this kind of applica-
tion, bulk materials are required due to the large mass
of magnetic refrigerant needed. However, there are some
niche applications which can work with a very limited
amount of refrigerant material, like the refrigeration of
electronic chips, microfluidic reactors and other devices
with small dimensions. For these latter applications, the
use of nanomaterials is feasible. This is why studies of
the MCE of nanostructured materials have become
increasingly popular in recent years [23–27].
The study of nanomaterials for magnetic refrigeration
started with superparamagnetic nanoparticles. There was
evidence of their improved performance when compared
with paramagnetic materials due to their enlarged mag-
netic moment [28–30]. However, their temperatures of
application were well below room temperature. These re-
sults induced researchers in the field of soft magnetic
nanocrystalline alloys to think that the transition from
ferromagnetism (at temperatures below the Curie temper-
ature of the matrix, T am
C ) to supermaramagnetism (at tem-
peratures above T am C ) [31,32] could give rise to good
magnetic refrigerants. Moreover, superparamagnetism
could be tuned to temperatures close to room temperature
by tuning T am
C [31]. Therefore, several attempts were made
to study the magnetocaloric response of soft nanocrystal-
line alloys of the Finemet and Nanoperm families, with
different alloying elements, to tune T am
C close to room tem-
perature, but the results for DS M were poorer than for the
paradigmatic Gd [33–35]. Neither jDS M j nor RC improve
through the nanocrystallization process [4,36]. However,
a deeper understanding of the magnetocaloric response of
multiphase materials and composites [18–20] has recently
allowed the development of nanocrystalline alloys in
which the refrigerant capacity is larger than that of its
amorphous precursor [21]. The guiding principle is to pro-
duce Gd-based nanocrystals inside the Gd-based amor-
phous precursor, as the Curie temperatures of both
phases are similar.
Another kind of nanomaterial is magnetic nanoparti-
cles, the MCE of which is not usually large, though the
peak covers a wide temperature span [37]. This can some-
times enlarge RC. In the case of materials with an FOPT
in the bulk, nanostructuring can produce a decrease in
MCE by losing the first-order character of the phase tran-
sition [38]. A special case is the effect associated with sur-
face spin disorder in core–shell nanoparticles, which
produces a sizeable MCE [23]; being a second-order or-
der–disorder transition, it can be studied using the tech-
niques developed for Curie transitions [27].
It has been shown recently that nanostructuring can
alter not only the quantitative response of a material,
but also its qualitative behavior, which can be com-
pletely different from that of its bulk counterpart [24].
 V. Franco, A. Conde / Scripta Materialia 67 (2012) 594–599
In the case of arrays of self-organized nanowires, the
application of the magnetic field perpendicularly to the
wire axis provokes a coexistence of positive and negative
MCE, whose sign and magnitude is controlled by the
magnitude of the field. This combination of direct and
inverse MCE was previously observed for other bulk
materials which underwent several different magnetic
transitions [39]. However, what is unique in the case of
the nanowires is that the sign of the MCE is controlled
by the magnitude of the applied field, and both positive
and negative DS M peaks take place for a single magnetic
transition. This opens new possibilities for the design of
completely new applications of the materials.
It is also interesting to note that the development of
multilayers with different compositions of each layer
(and therefore with a distribution of Curie temperatures)
can be used to enhance the magnetic field responsiveness
of MCMs in the H range appropriate for technological
applications [40,41]. In these cases, DS pk M has a linear
dependence on H in a broad temperature range close to
the transition temperature, which is an enhancement with
respect to the typical H0.7 behavior of bulk materials.
In summary, the magnetocaloric response of nano-
structured materials will not only depend on the charac-
teristics of the bulk material (the composition of the
phase), but will also be strongly dependent on other fac-
tors like particle size (and size distribution), particle con-
centration, interactions between particles, anisotropy and
finite size scaling, and a number of models have been pro-
posed to take these effects into account [24,25,42,43]. In
our opinion, the main interest of nanomaterials for mag-
netic refrigeration is the possibility of obtaining non-con-
ventional magnetocaloric responses which might give rise
to completely different applications of the effect, some of
them not envisaged yet.
5. Modeling the magnetocaloric effect in second-order
phase transitions
The simplest way to model the magnetocaloric re-
sponse of continuous phase transitions is to make use
of an equation of state and derive the thermomagnetic
properties from it. In particular, the Arrott–Noakes
equation of state [44]
1 1 1
H c ¼ aðT  T C ÞM c þ bM bþc
1
ð1Þ
where a and b are characteristic parameters of the mate-
rial under study and b and c are the critical exponents,
provides an appropriate description of the temperature
and field dependence of magnetization in the environ-
ment of the Curie transition of amorphous alloys. By
proper manipulation of Eq. (1), it has been demon-
strated that [45]
abc b1
DS M jT ¼T C ¼ bþcb H bþcþ1 ð2Þ
b bþc ð2b þ c  1Þ
It is not possible to get an analytical closed solution
for the magnetic entropy change for a broader tempera-
ture span, though it can be expressed as an integral of
magnetization [46] which does not imply derivatives:
Z M max  
1 c1
DS M ¼  acM aðT  T C Þ þ bM b dM ð3Þ
Ms
597
It has been demonstrated that the magnetocaloric re-
sponse of amorphous alloys can be properly modeled
across a relatively broad temperature range around TC
using this equation of state (Fig. 2) [45]. However, at tem-
peratures well below the transition, Eq. (1) is no longer va-
lid, as it implies, by using Eq. (3), a non-zero value of DS M
at 0 K, which is non-physical. Therefore, it is necessary to
find alternative equations of states which solve this discrep-
ancy. A recent attempt to tackle this problem [47]combined
the low temperature behavior of magnetization described
by a modification of the Handrich–Kobe equation, includ-
ing an asymmetric exchange fluctuation parameter [48],
with the high-temperature behavior described by the Ar-
rott–Noakes equation of state. This combination avoids
the low-temperature artifacts, but more work is needed
to improve the smoothness of the fitted curve across the
whole temperature range. Although, at first sight, the
description of the DS M curves at temperatures well below
TC might be considered irrelevant, the importance of this
open problem lies in the necessity of being able to model
the magnetocaloric response of multiphase composites
with a broad distribution of TC of the phases.
From Eq. (2) it is clear that the compositional evolution
of the magnetic entropy change peak should be described
by the prefactor of the field. However, this is a more com-
plicated expression than the previously mentioned phe-
nomenological linear relationship between DS pk M and the
magnetic moment found for some alloy series [12–15]. Fur-
ther studies of this apparent discrepancy are necessary.
6. Field dependence of the magnetocaloric effect in second-
order phase transitions
In recent years there has been an increasing number of
papers dealing with the field dependence of DS M . The rea-
son is not only academic, but is directly related to the pos-
sibility of comparing results measured under different
experimental conditions. Although the simplest and most
usual approach to compare the performance of different
materials is to quote DS pk M =H max for each alloy (which in-
volves making linear extrapolations and interpolations
of DS pk
M ), this gives rise to errors of the order of 30% in
making the comparison when changing the maximum
field from 1.5 T to 5 T. The appropriate solution to the
problem is to use power laws of the form DS pk M / H
n
[46,49]. There is, however, debate about what value
Figure 2. Magnetocaloric effect of the Fe77Cr8B15 amorphous alloy.
Experimental results: crosses; line: prediction of the Arrott–Noakes
equation of state. The inset shows the discrepancy at low temperatures.
598 V. Franco, A. Conde / Scripta Materialia 67 (2012) 594–599
the exponent n should take. Some authors claim that
second-order phase transitions materials should be repre-
sented by a mean field model which provides n = 2/3 [50],
and any deviation from that value should be explained by
the distribution of Curie temperatures of the material
[51,52]. We consider that not all materials can be repre-
sented by the mean field model of a Landau series expan-
sion and different materials will exhibit different values of
the critical exponents, with the relation between n and the
critical exponents given by n ¼ 1 þ 1=d ð1  1=bÞ. There
is a large body of experimental evidence to justify this
claim [45,49,53–57]. In fact, the field dependence of the
magnetocaloric effect has been proposed as an alternative
procedure to determine the critical exponents of materials
[56]. Both approaches (the mean field model with a distri-
bution of transition temperatures and the different critical
exponents) can represent the main features of the experi-
mental results, with some of the discrepancies with respect
to the experimental data being within the margin of exper-
imental error. Therefore, another interesting open prob-
lem is to determine unequivocally the best description of
the experimental results.
Whatever the explanation for the field dependence of
the magnetocaloric response, it will not affect the fact that
second-order phase transitions follow scaling laws and
that, if the magnetic entropy change or the adiabatic tem-
perature change are plotted vs. the appropriate axis, a uni-
versal curve for the magnetocaloric response can be
obtained [49,55]. Even if the analytical expression of the
equation of state is not known for a certain material, a
phenomenological procedure has been proposed that al-
lows us to construct the universal curve by using the
experimental data without the need to introduce a model
[46,49]. Its construction was based on the assumption
that, if such a universal curve exists, equivalent points
of the different DS M ðT Þ curves measured up to different
maximum applied fields should collapse onto the same
point of the universal curve. Therefore, the key is to iden-
tify which are the equivalent points of the different curves
for different fields. As the peaks (which in the mean field
case coincide at TC) should be in equivalent conditions,
we can assume that points which are at a certain level with
respect to the peak are also in equivalent magnetic states
(if this hypothesis was not correct, then we would not be
able to construct the universal curve). The temperatures
of these points will be denoted as reference temperatures
Tr, and their identification constitutes the first step of
the procedure. They fulfill the condition that
DS M ðT r Þ ¼ n DS pk
M , with a factor n smaller than 1 and
whose value is arbitrarily chosen (preferably close to or
higher than 1=2), which does not affect the procedure.
The second step is the normalization of the curves with re-
spect to their maximum. Finally, the temperature axis is
rescaled in such a way that the reference temperatures
are all at h ¼ 1 by using h ¼ ðT  T C Þ=ðT r  T C Þ. By
imposing the position of two points of each of the curves
(those at TC and at Tr), which implies three free parame-
ters, the whole curve collapses into a single universal
curve. This curve can be used for practical purposes, such
as making extrapolations of the results up to fields or tem-
peratures not available in the laboratory, enhancing the
resolution of the data and deconvoluting the response of
overlapping magnetic transitions. This universal curve
has been used to successfully determine the order of the
phase transition of materials for which the purely mag-
netic Banerjee criterion was giving erroneous results,
overcoming the need for complementary non-magnetic
measurements to make this determination. Currently, at-
tempts are underway to extend this universal curve to
materials with a first-order phase transition [58] and, even
if they are not based on the theory of critical phenomena,
the curves obtained could lead in the future to practical
applications in this field of research.
7. Concluding remarks
Magnetic refrigerant materials with a second-order
phase transition exhibit a smaller magnetic entropy
change peak than those with a first-order magneto-struc-
tural phase transition, but the refrigerant capacity of the
former can be comparable to or even larger than in the lat-
ter. Subsets of these materials with second-order phase
transitions are amorphous alloys, nanostructured materi-
als and composites. Amorphous alloys have the advanta-
ges of tunable Curie temperature, low cost, high electrical
resistivity and good mechanical properties, which are vir-
tues of the material in addition to their purely magnetoc-
aloric response. Open problems for this kind of material,
apart from improving the magnetocaloric response, are
the explanation of why transition metal-based amor-
phous alloys have an increasing magnetic entropy change
with increasing Curie temperature (a feature which con-
trasts with other crystalline and RE-based materials,
and which can be advantageous for some applications)
and the thorough study of the relationship between the
magnitude of the magnetic entropy change and the mag-
netic moment of the alloy (even if there are experimental
results which hint at a linear relationship, this is not justi-
fied by the models in use).
Nanostructured materials can be of use in niche appli-
cations of small-scale refrigeration, where there is no need
of using large amounts of refrigerant. It has been proven
that nanostructuring provides magnetocaloric responses
which are qualitatively and quantitatively different from
the bulk counterparts. We foresee an increase in alterna-
tive applications of the magnetocaloric effect once this
new behavior of the nanomaterials is understood in detail.
Measurement techniques for the direct determination
of the adiabatic temperature change have to be im-
proved to be able to measure these low mass materials,
in order to be able to check the model results.
Composites of materials with well known thermo-
magnetic properties are promising for obtaining en-
hanced magnetocaloric responses. Future work implies
enhancement of the modeling techniques and the cover-
ing of a broader range of the parameter space.
Fundamental problems and practical applications are
interlinked when studying the scaling behavior of the
magnetocaloric effect. More studies are needed to
unequivocally confirm the interpretation given to the
experimental results, as well as to extend the tempera-
ture range of the models. In particular, extending the
universal curves of the magnetocaloric effect to first-or-
der phase transition materials, even on a phenomenolog-
ical basis, can enhance the prediction capabilities of the
models used in refrigerator design.
 V. Franco, A. Conde / Scripta Materialia 67 (2012) 594–599
Acknowledgements
This work was supported by the Spanish Ministry of
Science and Innovation and EU FEDER (Project MAT
2010-20537), the PAI of the Regional Government of
Andalucı́a (Project P10-FQM-6462) and the United States
Office of Naval Research (Project N00014-11-1-0311).
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