MAGNETIC REFRIGERATOR

Magnetic refrigeration is a method of refrigeration based on the magnetocaloric effect. This

effect is defined as the response of a solid to an applied magnetic field which is apparent as a
change in its temperature.1 This effect is obeyed by all transition metals and lanthanide-series
elements. When a magnetic field is applied, these metals, known as ferromagnets, tend to heat
up. As heat is applied, the magnetic moments align. When the field is removed, the ferromagnet
cools down as the magnetic moments become randomly oriented. Gadolinium, a rare-earth
metal, exhibits one of the largest known magnetocaloric effects. It was used as the refrigerant
for many of the early magnetic refrigeration designs. The problem with using pure gadolinium
as the refrigerant material is that it does not exhibit a strong magnetocaloric effect at room
temperature. More recently, however, it has been discovered that arc-melted alloys of
gadolinium, silicon, and germanium are more efficient at room temperature.
The main difference associated with this process is that it is void of a compressor. The
compressor is the most inefficient and expensive part of the conventional gas compression
system. In place of the compressor are small beds containing the magnetocaloric material, a
small pump to circulate the heat transfer fluid, and a drive shaft to move the beds in and out of
the magnetic field. The heat transfer fluid used in this process is water mixed with ethanol
instead of the traditional refrigerants that pose threats to the environment. A majority of the
successful magnetic refrigeration research done to this point was completed by the Ames
Laboratory at the University of Iowa and by the Astronautics Corporation of America in
Madison, Wisconsin. Karl Gschneidner and Vitalij Pecharsky of the
Ames Laboratory and Carl Zimm of the Astronautics Corporation have led this research. The
team has developed a working system that uses two beds containing spherical powder of
Gadolinium with water being used as the heat transfer fluid. The magnetic field for this system
is 5 Tesla, providing a temperature span of 38 K. The maximum values obtained from this unit
include a cooling power of 600 Watts, Coefficients of Performance near 15, and efficiency of
approximately 60% of Carnot efficiency.3 Due to the high magnetic field, however, this system
is not applicable for use at home.
.

1
 WORKING OF MAGNETIC REFRIGERATION

The process flow diagram for the magnetic refrigeration system is shown in Figure 1. A
mixture of water and ethanol serves as the heat transfer fluid for the system. The fluid first
passes through the hot heat exchanger, which uses air to transfer heat to the atmosphere. The
fluid then passes through the copper plates attached to the non-magnetized cooler
magnetocaloric beds and loses heat. A fan blows air past this cold fluid into the freezer to keep
the freezer temperature at approximately 0F. The heat transfer fluid then gets heated up to 80F
as it passes through the copper plates adjoined by the magnetized warmer magnetocaloric beds,
where continues to cycle around the loop. However, the magnetocaloric beds simultaneously
move up and down, into and out of the magnetic field. The second position of the beds is shown
in Figure 2. Figure 3 shows how the cold air from the freezer is blown into the refrigerator by
the freezer fan, F-102. The temperature of the refrigerator section is kept around 39F.The cost
for mass production can be estimated using a learning curve.4Theequation used is shown as
Equation 1. Following the assumption that serving onehalf of the refrigerator market would
result in the production of 7 million refrigerators per year, and assuming a prototype cost of
$1000, it was found that the cost per unit would be approximately $500. This relationship is
presented in Figure. Magnetic refrigeration utilizes the magnetocaloric effect. This effect
causes a temperature change when a certain metal is exposed to a magnetic field. All transition
metals and lanthanide series elements obey this effect. These metals, known as ferromagnets,
tend to heat up as a magnetic field is applied. As the magnetic field is applied, the magnetic
moments of the atom align. When the field is removed, the ferromagnets cool down as the
magnetic moments become randomly oriented. Soft ferromagnets are the most efficient and
have very low heat loss due to heating and cooling processes.

2
Gadolinium, a rare-earth metal, exhibits one of the largest known magnetocaloric effects. Most
modern magnetic refrigeration designs employ arc-melted alloys of gadolinium, silicon, and
germanium, which provide greater temperature ranges at room temperatures. The presented
design utilizes such an alloy with the formulan Gd5(Si0.455Ge0.545)4. This alloy has a
temperature range of 12F to 80F.5 The typical household refrigerator has an internal volume
of 21 ft3, where the freezer represents approximately 30% of this volume. Freezers are designed
to maintain a temperature of 0F. Refrigerators maintain a temperature of 39F. The refrigerator
will be insulated with polyurethane foam, one of the most common forms of insulation
available.
The refrigerator is kept cool by forcing cold air from the freezer into the
refrigerator by using a small fan. The control system for maintaining the desired internal
temperatures consists of two thermostats with on/off switches. The freezer thermostat regulates
the temperature by turning the compressor off when the temperature gets below 0F. A second
thermostat regulates the fan that cools the refrigerator to 39F. To maintain a frost-free
environment in the freezer, a defrost timer will send power to a defrost heater on the coils for a
fifteen minute time period every eight hours. In the first six minutes, the walls of the freezer
will be defrosted. The water will then drain into a pan at the base of the refrigerator. The next
nine minutes involve the safety factor of not reaching a temperature in the freezer that is too
high. Also, a safety thermostat keeps the liquid water from freezing as it drains.
The heat transfer fluid for the magnetic refrigeration system is a liquid
alcohol-water mixture. The mixture used in the design consists of 60 % ethanol and 40 % water.
This mixture has a freezing point of 40F6, assuring that the mixture does not freeze at the set
operating temperatures. This heat transfer fluid is cheaper than traditional refrigerants and also
eliminates the environmental damage produced from these refrigerants. The temperature of the
fluid throughout the cycle ranges from 12F to 80F. The heat transfer fluid at approximately
70F gets cooled to 12F by the non-magnetized cold set of beds. This cooled fluid is then sent
to the cold heat exchanger, E-102, where it absorbs the excess heat from the freezer. This fluid
leaves the freezer at 0F. The warm fluid then flows through the opposite magnetized set of
beds, where it is heated up to 80F. This hot stream is now cooled by room temperature air in
the hot heat exchanger, E-101, to 70F. The cycle then repeats itself every three seconds after
the beds have switched positions. Copper tubing is used throughout the loop and in the two heat

3
exchangers. The two sets of beds, B-101 and B-102, contain the small spheres of
magnetocaloric size material. The of the beds resembles that of half of a soda can.

SELECTION OF REFRIGERANT

Modern cooling is almost entirely based on a compression/ expansion refrigeration cycle. It is a

high-energy demand industry with annual energy consumption measured in billions kWh. Over
the years, all parts of a conventional refrigerator, i.e. compressors, heat exchangers, refrigerants,
and packaging have been considerably improved due to an extensive research and development
effort, and in part by government edicts. This was made possible by a continuous dollar influx
from both federal and industrial sources. Both achieved and anticipated improvements of this
traditional technology, however, are incremental since modern refrigeration is already near its
fundamental limit of energy efficiency, which is well below the maximum theoretical (Carnot)
efficiency. Furthermore, the liquid chemicals used as refrigerants, eventually escape into the
environment promoting ozone layer depletion and global warming and, therefore, conventional
refrigeration ultimately promotes deleterious trends in the global climate. Other refrigerants,
such as ammonia, are hazardous chemicals. The interest in magnetic cooling is continuing to
grow rapidly. This can be attested to by the fact that in September 2005, the first international
conference on magnetic

temperature was held in Montreux, Switzerland. The next conference was in April 2007.The
magnetocaloric effect (MCE) is the response of a magnetic solid to the application (or removal)
of a magnetic field, which is evident by a change in the temperature of the solid. For a
ferromagnetic material near its magnetic ordering temperature (the Curie temperature [T ]),
when a magnetic field is applied, the unpaired 4f or 3d spins are aligned
the magnetic field, which decreases the entropy in the isothermal process or causes the sample
to warm up in the adiabatic process. When the magnetic field is turned off the spins randomize
increasing the entropy, or the material cools. A few materials, primarily antiferromagnetic
compounds, may exhibit the opposite behavior; they cool when a magnetic field is applied, and
warm up when the field is removed. The temperature change is called the adiabatic temperature

4
of the magnetic field change. At low field, <20 kOe, the two parameters vary nearly linearly
with the magnetic field, but at fields >20 kOe the MCE change per unit magnetic field change
becomes somewhat smaller as the field increases, i.e. the slope deviates from the linearity
established at lower fields. Because of this dependence the efficiency of magnetic cooling
increases with increasing field.Thus one wants as large a magnetic field as possible in the
magnetic cooling device. However, there are some practical considerations which need to be
taken into account. For example, a superconducting magnet can easily be designed to provide a
magnetic field of 50 to 70 kOe (5 to 7 T) at a reasonably modest cost, but such a magnetic field
source is impractical for household applications and most transportation methods. The only
practical magnetic field source for household and transportation applications is the high energy
Nd Fe B permanent magnet which can deliver a magnetic field of 12 to 15 kOe for areasonable
gap size between the pole pieces to allow one to move the magnetic refrigerant material in and
out of the magnetic field.
Applications which would utilize the rare earth permanent magnets are: household
refrigerator/freezers; household air conditioning; automotive, aircraft, small seafaring vessels
for climate control (both heating and cooling, and humidity); portable coolers; active cooling of
electronics; portable refrigerators (medical).The use of a superconducting magnet source is the
only practical way for large scale applications, such as supermarket chillers; frozen food plants;
building climate control (heating, cooling and humidity) such as office buildings, apartments,
convention centers, meeting halls; and climate control for large seafaring vessels.. The amount
of magnetic refrigerants required will range from 0.01 to 100 kg per cooling device. The
smaller quantity would be for small refrigerators and coolers noted above, while the larger
kilogram quantities are required in the magnetic cooling machines for large scale applications.
Thus magnetic refrigeration, even before it matures, will be the biggest rare earth market. This
is especially true for the small scale units since both the magnetic refrigerant material and the
permanent magnet will contain significant amounts of rare earth metals per cooling unit.

5
 ROOM TEMPERATURE MAGNETIC REFRIGERATION

Nearly all refrigeration devices work by compressing and then decompressing gases. But thanks to
research at the U.S. Department of Energys Ames Laboratory, that technology may one day be
replaced by an entirely different cooling method, one that uses permanent magnets and specialized
alloys. The result would be refrigerators, air conditioners and giant warehouse freezers that are
greener, quieter and far more energy efficient than their predecessors. Magnetic refrigeration works
because of a phenomenon known as the magnetocaloric effect that was discovered

The first was a newly designed permanent magnet created by Ames Lab researchers David Jiles
and Seong-Jae Lee, along with Pecharsky and Gschneidner. Their magnet was configured in
such a way as to produce a magnetic field nearly double that of previous designs. This greatly
enhanced the devices efficiency.
To further enhance a magnetic refrigerators efficiency, Gschneidner and Pecharsky needed to
boost gadoliniums magnetocaloric effect. They and their colleagues did this by adding silicon

6
and germanium to the metal. Equally important, the resulting Gd5Si2Ge2 alloy was produced
using commercial grade gadolinium (as opposed to research grade) via a process the Ames
Laboratory researchers devised. This enabled the team to create larger quantities of the

7
material, and it suggested that commercial-scale production of the gadolinium alloy could be
done economically.

As a next step, the Ames Lab team

incorporated their groundbreaking
magnet and gadolinium alloy into a
prototype device, developed in
collaboration with Astronautics
Corporation of America. The
refrigerator consists of a wheel that
contains sections filled with the
gadolinium alloy. The wheel
revolves around a high-powered,
rare-earth permanent magnet.

As it revolves, it passes through a gap in the magnet at the precise point where the magnetic
field is concentrated. When exposed to this field, the gadolinium alloy in the wheel heats up.
After entering the field, water is circulated to draw the heat out of the metal. As the gadolinium
alloy leaves the magnetic field, the material cools further. A second stream of water is itself
cooled by the gadolinium alloy. This water is then circulated through the refrigerators cooling
coils.

8
 REFRIGERANT MATERIALS

Gadolinium metal is considered the prototype magnetic refrigerant material for near room
temperature magnetic refrigerators. It is a good refrigerant, but to make magnetic refrigeration
even more efficient it is important to have an array of materials with better MCE properties than
Gd. Of course, there are other ways to increase the efficiency, such as new and better
thermodynamic cycles, improved engineering designs, increase the number of AMR cycles per
unit time, better heat transfer fluids. Since the discovery of the GMCE in the
However, at room temperature depending on x three different crystallographic
phases are observed. For x > 0.55 the aforementioned Gd5Si4 structure is stable, for x < 0.3 the
materials adopt the Sm5Ge4-type structure with the same space group (Pnma) but a different
atomic arrangement and a somewhat larger volume, finally in between these two structure types
the monoclinic Gd5Si2Ge2 type with space group (P1121/a) is formed, which has an
intermediate volume. The latter structure type is stable only below about 570K where again the
orthorhombic Gd5Si4-type structure is formed in a first-order phase transition. As one may
guess, the three structure types are closely related; the unit cells contain four formula units and
essentially only differ in the mutual arrangement of identical building blocks which are either
connected by two, one or no covalent-like Si-Ge bonds, resulting in successively increasing
unit-cell volumes. The giant magnetocaloric effect is observed for the compounds that exhibit a
simultaneous paramagnetic to ferromagnetic and structural phasetransition that can be either
induced by a change in temperature, applied magnetic field or applied pressure In contrast to
most magnetic systems the ferromagnetic phase has a 0.4% smaller volume than the
paramagnetic phase which results in an increase of Tc on application of pressure with about
3K/kbar.
The structural change at the phase transition brings along also a very large magneto-
elastic effect and the electrical resistivity behaves anomalous. The strong coupling between
lattice degrees of freedom and magnetic and electronic properties is rather unexpected,
because the magnetic moment in Gd originates from spherical symmetric s-states that in

9
contrast to other rare-earth elements hardly couple with the lattice. First principle electronic
structure \couplingvariationally, could reprodce some distinct features of the phase transition
Another interesting type of materials are rare-earth - transition-metal
compounds crystallizing in the cubic NaZn13 type of structure. LaCo13 is the only binary
compound, from the 45 possible combinations of an rare-earth and iron, cobalt or nickel, that
exists in this structure. It has been shown that with an addition of at least 10% Si or Al this
structure can also be stabilized with iron and nickel[24]. The NaZn13 structure contains two
different Zn sites. The Na atoms at 8a and ZnI atoms at 8b form a simple CsCl type of structure.
Each ZnI atom is surrounded by an icosahedron of 12 ZnII atoms at the 96i site. In La(Fe,Si)13
La goes on the 8 a site, the 8b site is fully occupied by Fe and the 96i site is shared by Fe and
Si. The iron rich compounds La(Fe,Si)13 show typical invar behavior, with magnetic ordering
temperatures around 200K that increase to 262K with lower iron content[25]. Thus, though the
magnetic moment is diluted and also decreases per Fe atom, the magnetic ordering temperature
increases. Around 200K the magneticordering transition is found to be also distinctly visible in
the electrical resistivity, where a chromium-like cusp in the temperature dependence is
observed. In contrast to Gd5Ge2Si2 this phasetransition is not accompanied by a structural
change, thus above and below Tc the material is cubic. Recently, because of the extremely sharp
magnetic ordering transition, the (La,Fe,Si,Al) system was reinvestigated by several research
groups and a large magnetocaloric effect was reported
The largest effects are observed for the compounds that show a field-
or temperature-induced phase-transition of first order. Unfortunately, these large effects only
occur up to about 210 K as the magnetic sublattice becomes more and more diluted. When
using standard melting techniques, preparation of homogeneous single-phase samples appears
to be rather difficult especially for alloys with high transition metal content. Almost single
phase samples are reported when, instead of normal arc melting, rapid quenching by melt
spinning and subsequent annealing is employed Samples prepared in this way also show a very
large magnetocaloric effect. To increase the magnetic ordering temperature without loosing too
much magnetic moment, one may replace some Fe by other magnetic transition-metals.
Because the isostructural compound LaCo13 has a very high critical temperature substitution of
Co for Fe is widely studied. The compounds and

10
and thus a very high transition-metal content, show a considerable magnetocaloric effect near
room temperature[32-35]. This is achieved with only a few percent of Co and the Co content
can easily be varied to tune the critical temperature to the desired value.
It should be mentioned however that near room temperature the values
for the entropy change steeply drop. Hydrogen is the most promising interstitial element. In
contrast to other interstitial atoms, interstitial hydrogen not only increases the critical
temperature but also leads to an increase in magnetic moment[27, 36-40]. The lattice expansion
due to the addition of three hydrogen atoms per formula unit is about 4.5%. The critical
temperature can be increased to up to 450K, the average magnetic moment per Fe increases
from 2.0 B to up to 2.2 B and the field- or temperature-induced phase-transition is found to
be of first-order for all hydrogen concentrations. This all results for a certain Si percentage in an
almost constant value of the magnetic entropy change per mass unit over a broad temperature
span. From the materials cost point of view the La(Fe,Si)13 type of alloys appear to be very
attractive. La is the cheapest from the rare-earth series and both Fe and Si are available in large
amounts. The processing will be a little more elaborate than for a simple metal alloy but this can
be optimized. For the use in a magnetic refrigerator next to the magnetocaloric properties also
mechanical properties and chemical stability may be of importance. The hydrogenation process
of rare-earth transition-metal compounds produces always granular material due to the strong
lattice expansion. In the case of the cubic NaZn13 type of structure this does not seem to be the
case. At the phase transition in La(Fe,Si)13 type of alloys also a volume change of 1.5% is
observed[41]. If this volume change is performed very frequently the material will definitely
become very brittle and probably break in even smaller grains. This can have distinct influence
on the corrosion resistance of the material and thus on the lifetime of a refrigerator. The
suitability of this material definitely needs to be tested.

of first order [61]. The magnetic-ordering transition from the paramagnetic state to the
ferromagnetic state is accompanied by a discontinuous change of the volume of 0.05%. Thus,
the ferromagnetic state has a higher volume than the paramagnetic one. This phase transition is
found to be extremely sensitive to changes in pressure or magnetic field. Application of
pressure first reduces the Curie temperature and at pressures exceeding 5 kbar antiferromagnetic
ordering preceding the ferromagnetic ordering is observed [62]. Substitution of As, B or Si into

11
the P sublattice results in an increase of the Curie temperature [63], which can easily be lifted to
above room temperature for As or Si concentrations of 10% or by 4% of
B. Substitution of Mn for Fe on the 3g sites further increases the magnetic moment to about 4
B. To stabilize the Fe2P-type of structure, simultaneously to the Mn substitution also part of
the P should be replaced.
The most extensively studied series of alloys is of the type MnFe(P,As).
The magnetic phase diagram for the system MnFeP-MnFeAs [64] shows a rich variety of
crystallographic and magnetic phases. The most striking feature is the fact that for As
concentrations between 30 and 65% the hexagonal Fe2P type of structure is stable and the
ferromagnetic order is accompanied by a discontinuous change of volume. While the total
magnetic moment is not affected by changes of the composition, the Curie temperature
increases from about 150 K to well above room temperature. We reinvestigated this part of the
phase diagram [65, 66] and investigated possibilities to partially replace the As [67-69]. The
large MCE observed in Fe2P based compounds originates from a field-induced firstorder
magnetic phase transition. The magnetisation is reversible in temperature and in alternating
magnetic field. The magnetic ordering temperature of these compounds is tuneable over a wide
temperature interval (200 K to 450K). The excellent magnetocaloric features of the compounds
of the type MnFe(P,Si,Ge,As), in addition to the very low material costs, make it an attractive
candidate material for a commercial magnetic refrigerator. However same as for MnAs alloys it
should be verified that materials containing As do not release this to the environment. The fact
that the magneto-elastic phase-transition is rather a change of c/a than a change of volume,

makes it feasible that this alloy even in polycrystalline form will not experience severe aging
effects after frequent magnetic cycling.

12
 SELECTION OF MAGNETS

Reasonable gap size between the pole pieces to allow one to move the magnetic refrigerant
material in and out of the magnetic field. Applications which would utilize the rare earth
permanent magnets are: household refrigerator/freezers; household air conditioning;
automotive, aircraft, small seafaring vessels for climate control (both heating and cooling, and
humidity); portable coolers; active cooling of electronics; portable refrigerators (medical).
The use of a superconducting magnet source is the only practical way for
large scale applications, such as supermarket chillers; frozen food plants; building climate
control (heating, cooling and humidity) such as office buildings, apartments, convention
centers, meeting halls; and climate control for large seafaring vessels. As far as we are aware no
one has designed, built and tested a large scale cooling machine or even a prototype apparatus.

13
 OBSTACLES TO COMMERCIALISATION

As noted above at least 20 laboratory scale prototype magnetic refrigerators have been built
and tested, but there are still a number of obstacles which need to be overcome for successful
large scale commercialization. The main obstacles are as follows, but they are not listed in any
priority.

Magnetic refrigerants, which have a second order magnetic transition, with better MCE
properties than Gd would give a big boost towards moving this technology to large scale
production of magnetic cooling devices. This is especially true if the costs associated with
forming the final regenerator material (spheres, wires, foils) are not much more expensive than
it costs to make Gd foils and/or spheres and/or wire mesh.
The production of large quantities of the magnetic refrigerant, tons per day at a
reasonable cost is critical. Most of the materials studied to date have only been prepared in
Permanent magnets which have higher magnetic strength and lower costs will benefit the
commercialization. As much as one-third of the cost of a magnetic refrigerator is the magnet
source. Improved magnetic field strength will lead to high efficiencies, and this will allow the
engineer to reduce the size of the permanent magnet array for the same amount of cooling.
Engineering considerations should be examined closely to improve the efficiency. These
improvements could involve: the heat flow from the cold object to the hot heat exchanger; the
heat exchanger themselves; increasing the cycle frequency; and the heat exchange fluid, etc.
The AMR thermodynamic cycle is considered to be the best cooling cycle today for
magnetic cooling/heating, but it is possible by making some modifications it could be improved.
New thermodynamic cycles, especially to take into account the MCE behaviors of first order
magnetic transitions, would be a big step forward to utilize their unique properties in a practical
magnetic refrigerator. The first order magnetic transformation materials have a large MCE (i.e.
GMCE) due to the fact that in addition to normal magnetic entropy associated with magnetic
ordering, there is a second contribution, the entropy associated with the structural change in
materials which exhibit a magnetic-structural transformation. The magnitudes of the two
entropies are comparable. There are several problems associated with such material, one of
which is the hysteresis inherently associated with first order transitions. It may be possible to

14
reduce the hysteresis, but never eliminate it, by increasing the purity, and/or grain size, and
perhaps by

15
 IMPACT ON RARE EARTH MARKET

Magnetic refrigeration will have a tremendous impact on the rare earth markets as this
technology grows and matures. We believe that the first commercial units will be on the market
within a few years. How rapidly this market will grow is difficult to predict. In part it will
depend upon the speed at which some of the impediments to commercialization, see below, are
overcome. The amount of magnetic refrigerants required will range from 0.01 to 100 kg per
cooling device. The smaller quantity would be for small refrigerators and coolers noted above,
while the larger kilogram quantities are required in the magnetic cooling machines for large
scale applications.
For refrigerators which will use permanent magnets as the power source we believe 0.5 to 100
kg of the Nd Fe B alloy are required per refrigerator or cooling device.


Applications

Applicable for home air conditioners and refrigerators to supermarket freezers

Naval vessels to cool electronic systems
Extracting and liquefying hydrogen, makes it economically viable to produce the fuel
Liquefaction of natural gas
 Future Developments

Magnetic refrigerants, which have a second order magnetic transition, with better MCE
properties than Gd-alloys would give a big boost towards moving this technology to
home refrigerators.
Permanent magnets which have higher magnetic strength and lower costs will benefit the
commercialization. As it improves efficiency, reduce size of equipment and maintenance
cost.
24

REFERENCE

ieeexplore.ieee.org/iel5/6/20789/00963241.pdf
en.wikipedia.org/wiki/Magnetic refrigeration
http://www.ameslab.gov/news/inquiry/fall97/bigchill.html
http://www.ameslab.gov/files/MagFridge_Foundation.pdf
www.che.cemr.wvu.edu%2Fpublications%2Fprojects%2Fpr frigerator.pdf
http://www.intalek.com/Index/Projects/Research/MagneticRefrigeration.PDF
http://ipnpr.jpl.nasa.gov/progress_report/42-78/78D.PDF
http://www.eurekalert.org/features/doe/2001-11/dl-mrs062802.php
http://www.amestrib.com/articles/2011/01/18/ames_tribune/news/doc4d35ad240476773
3627797.txt
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