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Article history: Ensure wellbeing for each of us is a first necessity for peace and development of society
Received 16 April 2013 while preserving the environmental balance of the blue planet. Today’s society is faced
Received in revised form with major challenges such as the supply of energy, water, food, etc. Refrigeration is an
15 September 2013 important factor in the modern world. It is vital before life (sperm banks), for life (con-
Accepted 16 September 2013 versation food, medicine, .), and after life (preservation of human organs and tissues).
Available online 26 October 2013 However the negative impact of refrigeration on the environment is visible and, conse-
quently, refrigeration systems are subject to prescriptive regulation. This regulation pro-
Keywords: vides a great opportunity for the emergence of new refrigeration technologies and new
Conventional refrigeration product markets. In recent years, magnetic refrigeration is considered as a serious alter-
Refrigerants native for conventional systems. Today proof of the concept is established. Therefore what
Magnetic refrigeration remains is to provide systems for the society.
Magnetocaloric material ª 2013 Elsevier Ltd and IIR. All rights reserved.
Magnetic field sources
1. Introduction U.S. still exported 25 million tons of ice per year. Sometimes
the natural snow was mixed with salt in order to reach low
The use of ice for prolonging the storage life of foodstuff dates temperatures (from 1600). The production of ice cream is
back many millenniums. Ice owes its effectiveness as a cool- known to be done according to this technology in ancient
ing agent to its constant melting point of 0 C. In order to melt, Rome. However, the pollution of lakes, the competitiveness of
ice must absorb 333 kJ kg1. Up to the middle of the last cen- the new technology and no able to follow the increase of the
tury all ice used for cooling was from natural sources. This ice demand has caused end of this industry.
was taken from lakes in winter and then stored. In 1890, the Refrigeration is the process of removing heat from an
enclosed volume or from a substance, to elsewhere for the
* Corresponding author.
E-mail address: Osmann.sari@heig-vd.ch (O. Sari).
0140-7007/$ e see front matter ª 2013 Elsevier Ltd and IIR. All rights reserved.
http://dx.doi.org/10.1016/j.ijrefrig.2013.09.027
i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 7 ( 2 0 1 4 ) 8 e1 5 9
Nomenclature W Work J
hexerg Exergetic efficiency e
B Magnetic induction Tesla, T
COP Coefficient of performance - Subscript
h Specific enthalpy J kg1 Aux Auxiliaries
MCE Magnetocaloric effect K C Curie
p Pressure bar Cool Cold side
Q Energy transfer J Heat Hot side
s Specific Entropy J (kg K)1 M magnetic
T Temperature K, C
primary purpose of lowering the temperature of the enclosed In 2006, the Mobile Air Conditioning Directives (MAC) was
space or substance and then maintaining that lower temper- adopted in the EU. The main objective of the directives con-
ature (Lawrence, 2003). There are two processes of production sists the use of greenhouse gases with a GWP less than 150.
of the cold: the physical process of change of state with The HFO-1234yf was proposed in order to replace HFC-134a as
compression then relaxation and physical-chemical process a refrigerant in mobile air conditioning system.
(absorption system). In France, Ferdinand Carré developed a In order to be free from synthetic refrigerants, industries
the first cooling system with ammonia and water. The first are continuously searching for environmentally friendly and
machine of refrigeration with compression was proposed by suitable new technologies that will enable high energy sav-
Jacobs Perkins in 1834 which used ether as refrigerant. In 1913, ings, therefore reducing indirect CO2 emissions.
the first domestic refrigerator was built. In 1929, DuPont in- During the last fifteen years both the load reduction of the
vents CFCs (chlorofluorocarbons), marketed under the name refrigerants in the installations and the use of natural,
“Freon”. Dichlorodifluoromethane (CCl2F2) is odorless, nonflammable, environmentally friendly refrigerants have
nonflammable and presents a low toxicity. In 1931, the first been the preferred options by many end users such as Nestlé,
industrial manufacturing was realized by Electrolux. The in- Unilever, Coca Cola, etc.
dustry was driven by the development of electricity produc- The research on the future technologies orients itself to-
tion and the growth of the electric motors production. ward the ice slurry refrigeration (indirect cooling technology),
The refrigeration industry achieved a major development vapor compressor technology (hydrocarbons, CO2, ammonia,
with the arrival of refrigerants like CFC-R12, HCFC-R22 (1935) HFOs), thermal electric refrigeration, thermal acoustic refrig-
and CFC-R502 (1961), HFC R134 (1993), etc. The HFCs have no- eration and magnetic refrigeration (MR).
ozone depletion advantages over R22; however, they still have Active magnetic refrigeration system is considered actually
some global warming potential impact (GWP). The required as an attractive alternative for conventional vapor compres-
characteristics for a refrigerant are: environmental accept- sion refrigeration systems. In the last decade two research
ability, chemical stability, materials compatibility, topics emerged in this domain. The first one is devoted to the
refrigeration-cycle performance, non-flammability and non- development of new materials with high performances (MCE,
toxicity, boiling point, etc. DSm), and the second concerns the design and building effi-
Refrigeration is an important key in the modern world and cient magnetic cooling devices. From the 2000’s the discovery
it is in a continuous to progress. In 2007, domestic refrigera- of the high polarization permanent magnet in Nd-Fe-B and of
tion accounts for over 27 million devices in France. In 2007, the the giant MCE (Pecharsky and Gschneidner, 1997), several
energy consumption of freezer refrigerators represents 21% of demonstration units have been developed (Yu et al., 2010)
total electricity consumption in France, i.e 18 billion kWh from, Canada, China, Denmark, France, Switzerland, USA, etc.
consumed and an equivalent of 2.25 billion tons of CO2
(ADEME, 2007).
From 1973, the presence of CFCs in the atmosphere is re- 2. Conventional refrigeration
ported. Since then refrigeration occupies scientists and poli-
tics. The environmental protection is one more challenge to A system consists of several components combined together
overcome. Refrigeration techniques are the focus of two is- in order to obtain a given result. The thermodynamic cycle is
sues. Firstly the destruction of the ozone layer (CFC, HCFC), defined by the succession of thermodynamic states. For a
secondly the intensification of greenhouse gases (CFC, HCFC machine working continuously it is necessary to assign to
and HFC). These two preoccupations have given rise to the each of the thermodynamic transformations the inverse
Montreal and Kyoto protocols. transformation. Cold production uses the endothermic phe-
These international regulations provide a great opportunity nomenon: vaporization of a liquid (Fig.1). The thermodynamic
for the emergence of new refrigeration technologies and new cycle used in the most common refrigerator is the gas-
products. Consequently, more efficient refrigerants and equip- compression/expansion method. The ideal thermodynamic
ments were developed in recent years. In addition, the impact of cycle of the refrigeration is shown in Figs. 1a and b. This
synthetic refrigerants on the environment as well as the legal technology, existing since 1920s, has the advantage to be
safety obligations drive the refrigeration industry to seek for mature, cheap and well controlled (compressor, refrigerant,
new ways for completely phasing out greenhouse gases or for oil). However, its performance is still low. Since Montreal
decreasing their charge in miscellaneous installations. protocol (1987) many works have been carried out in order to
10 i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 7 ( 2 0 1 4 ) 8 e1 5
3. Magnetic cooling
ODP GWP Volume capacity % e CHF/Kg ATEL toxicity LFL inflammability limite
(ref. CFC-R12) (ref. HCFC R22, 2012) limite
Fig. 4 e A map for different groups working on the magnetocaloric refrigeration around the world (left), and the maximum
obtained temperature span (right).
firstly used by Brown (1976) in 1976 and then its magneto- (Tegus et al., 2002), MnAs1 xSbx (Wada and Tanabe, 2001) and
caloric and physical properties were widely studied. LaFe13 xSix (Hu et al., 2002; Fujita et al., 2003; Balli et al., 2007)
The use of gadolinium as active material has various dis- have been reported and intensively investigated. Tegus et al.
advantages. First, the price of Gd is very high (w4000 $/kg). (2002), have demonstrated that MnFeP0.45As0.55 exhibits a
Second, Gd has a poor resistance to corrosion and oxidation in large change of magnetic entropy at around 300 K with the
water which affects its magnetocaloric properties and de- similar value with Gd5Ge2Si2. Further, it was shown by Wada
creases the magnetic cooling machine performance. Finally, and Tanabe (2001) that MnAs possesses a giant magneto-
the cooling range is limited close to the room temperature caloric effect close to 318 K. For a field variation from 0 to 2 T,
where the magnetocaloric effect is very large (on account of the resulting entropy change is about 30 J kg1 K1, six times
the 2nd order transition occurring at 294 K). higher than gadolinium. In addition the substitution of 10% Sb
In 1997, the discovery of the giant magnetocaloric effect for As in MnAs compound reduces the thermal hysteresis and
(GMCE) in Gd5Ge2Si2 and its derivatives (Pecharsky and lowers the Curie temperature to 280 K, while the giant MCE is
Gschneidner, 1997) with a two times larger entropy variation retained.
compared to Gd, has revolutionized the interest in the Although the cited materials present excellent magneto-
research on new magnetocaloric materials and the develop- caloric properties, the costs of the constituent elements (Gd,
ment of new magnetic cooling systems. At TC ¼ 276 K and for a Ge) as well as the large amount of hysteresis due to the first
magnetic field variation from 0 to 5 Tesla, the magnetic en- order character of the magnetic transition, remain serious
tropy change is about 18.5 J (kg K)1 (9.8 J (kg K)1 for Gd). This obstacles for their implementation. However, for some Mn-
large value results from the first order magneto-structural based compounds, the presence of the toxic elements As
transformation at the Curie point. Later, materials with a and/or P that have high vapor pressure which makes the
first-order magnetic phase transition such as MnFeP1 xAsx production of these materials an additional challenge and will
Fig. 5 e Magnetic field distribution inside the developed magnetic field source.
i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 7 ( 2 0 1 4 ) 8 e1 5 13
add additional costs in manufacturing the magnetic refrig- The rotary system is constituted of two 1.5 Tesla modified
erant. Instead, among all the reported magnetocaloric mate- Halbach magnets which rotate while the 12 magnetocaloric
rials, LaFe13 xSix (Hu et al., 2002; Fujita et al., 2003; Balli et al., beds remain fixed. The cooling machine reaches a maximum
2007) has been shown to be the most promising alternative temperature span of 11 K and produces a cooling power of
due to their large magnetocaloric effect and low hysteresis. In 220 W. In this refrigerator, the two magnetic sources are ar-
addition, the low cost of the elements comprising the com- ranged so that the moment of inertia of the magnet is mini-
pounds (Fe) makes this family of materials very interesting. mized and inertial forces are balanced. The heat transfer fluid
It has been demonstrated that LaFe13 xSix exhibit a flow is driven by a continuously running pump and is
thermally induced first order magnetic transition from the switched by four rotary valves to the appropriate beds as the
ferromagnetic to the paramagnetic state at low temperatures magnet rotates. Another interesting system is the prototype
(at around 200 K). The field induced itinerant electron meta- built and presented by Tura and Rowe at the Thermag II
magnetism (IEM) transition occurs just above TC in the same conference (Tura and Rowe, 2007). The rotary permanent
temperature range leading to GMCE. In addition, for practical magnet refrigerator utilizes two pairs of concentric Halbach
application it is necessary to shift the Curie point toward room arrays which are synchronized such that one magnetocaloric
temperature while retaining large MCE. In this way, by bed is being demagnetized while the second one is being
studying the effect of interstitial hydrogen on the LaFe13 xSix, magnetized. The generated magnetic induction of a 20 cm3
Fujita et al. (Fujita et al., 2003) found that the TC can be cylindrical volume is about 1.4 Tesla. The maximum obtained
adjusted between 190 and 330 K (room temperature included) temperature span is approximately 13 K. The system is
without compromising the large MCE. For example, the ob- designed to operate at a frequency as high as 5 Hz. A detailed
tained DSm under 2 Tesla is about 20 J (kg K)1 for La(Fe0.88- review on the recent reported magnetic cooling systems can
Si0.12)13Hy which is four times higher compared to gadolinium be found in (Yu et al., 2010).
(w5 J (kg K)1 for 2 Tesla). Among all the reported prototypes, the pre-industrial
On the other hand, by increasing the hydrogen content (y), magnetic cooling system developed more recently at the
the adiabatic temperature change has been enhanced by HES-SO Yverdon-Les-Bains (Balli et al., 2010), is one of the
about 50% when y ¼ 1.5 (TC ¼ 323 K) compared with y ¼ 0 most innovative machine. Based on the permanent magnets
(TC ¼ 195 K). Later, the hydrided compounds have been tested
in a magnetic refrigerator with encouraging results (Zimm
et al., 2007). However, the chemical as well as the mechani-
cal instability of hydrides remain a serious obstacle for a
commercial use. In order to avoid this inconvenience and as
underlined for example in Balli et al. (2007), La(Fe, Co)13 xSix
with a small amount of cobalt appears as the most attractive
alternative. Fig. 7 displays temperature dependences of the
normalized magnetocaloric effect. This latter is about 2 K T1
which is comparable with that of gadolinium (2.5 K T1).
Fig. 8 e A general view of the developed magnetic refrigerator (a), and a schematic picture of the implemented AMR cycle
with the new design of the regenerator (b).
array described above, the device was built taking into ac- the needed mechanical energy during magnetization-
count the compactness, the market, and the thermodynamic demagnetization process can be saved which increases the
performance requirements. It is designed to produce a cooling coefficient of performance (COP).
power of about 100 Watt with a temperature span larger than \Besides, to reach a large temperature span between the
20 K. Plates of gadolinium metal were first used as the mag- hot and the cold sources, a modified Active Magnetic
netic refrigerant. This is mainly attributed to the ability of Gd Refrigeration (AMR) cycle was adopted and adapted to the
to answer the engineering requirements (ductile), its avail- new configuration of the regenerator. Fig. 8 shows a general
ability on the market, and its room temperature magneto- view of the developed device. This latter is constituted of two
caloric performance. However, other materials are actually magnetic sources to double cooling power, four heat ex-
under test. changers and two regenerators with MC plates. The magne-
To increase the magnetic systems efficiency, many ef- tocaloric blocks movement is driven by a linear actuator. In
forts were made to reduce the magnetic forces in the ma- Fig. 9, we present an example of the obtained temperature
chine. For this purpose, a new design in which the active span (30 K) between hot and cold sources, after a number of
material is divided into two separated parts was proposed AMR cycles.
(Fig. 8b). Therefore, when the first block is magnetized the
rest of the magnetocaloric refrigerant is simultaneously
demagnetized, leading then to the compensation of the
4. Conclusions
magnetic forces. The numerical calculations have demon-
strated that with the new configuration of the magneto-
The Montreal and Kyoto regulations have opened the way for
caloric materials, the resulting force in the cooling machine
the emergence of new refrigeration technologies and new
can be markedly reduced (Balli et al., 2011). The experi-
product markets.
mental measurements of the magnetic force performed on
From Warburg, Edison and Tesla, Weiss and Piccard, Debye
our developed machine have confirmed the simulation re-
and Giauque, and recently Brown, Steyert, Gschneidner and
sults. The calculations demonstrate that more than 90% of
other scientists, magnetic refrigeration near room tempera-
ture becomes alive and today a proof of the concept is
established.
The various developed demonstrators let us foresee the
importance of various components such as MCM shape, direct
cycles or regeneration cycles, nature of the cooling fluid,
magnetic field, heat exchangers, pressure drops, etc. The
development of new materials with high magnetocaloric
performance makes it possible to deal with the requirements
of technical applications. In addition question as how to
improve magnetic field, the regeneration efficiency and the
heat transfer efficiency should be also considered.
Based on the obtained results by different groups, mag-
netic refrigeration is a promising technology. However,
although the future of magnetic cooling is bright, there are
still a number of challenges.
The gap to be bridged in going from MCE principle to a
competitive device that meets the user’s needs is then
demanding but constitutes a rich and exiting experience for
Fig. 9 e Example of the obtained temperature span. both, scientists and engineers.
i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 7 ( 2 0 1 4 ) 8 e1 5 15
Hu, F.X., Shen, B.G., Sun, J.R., Wang, G.J., Cheng, Z.H., 2002. Very
Acknowledgements large magnetic entropy change near room temperature in
LaFe11.2Co0.7Si1.1. Appl. Phys. Lett. 80, 826e828.
We further are grateful to State of Canton de Vaud, Kitanovski, D. Vuarnoz, M. Diebold, C. Gonin, P.W. Egolf, 2008,
Switzerland, OFEN e Switzerland, the University of Applied Application of magnetic refrigeration and its assessment,
Annual report 2007, Bundesamt für Energie BFE 2008.
Sciences of Western Switzerland (HES-SO-Yverdon-les-Bains),
Lawrence, Jesse N., 2003. Refrigeration Fundamentals throughout
INTERREG IV-A France Suisse. We acknowledge their financial History: Methods Used to Obtain Colder Temperatures, and
support. Principles Governing Them. A literature Seminar, The
University of Alabama.
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