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MAGNETIC REFRIGERATION TECHNOLOGY


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5th International Advanced Technologies Symposium (IATS’09), May 13-15, 2009, Karabuk, Turkey

MAGNETIC REFRIGERATION TECHNOLOGY APPLICATIONS ON NEAR-


ROOM TEMPARATURE

Engin GEDİK a, * Muhammet KAYFECİb Ali KEÇEBAŞc Hüseyin KURTd


a, *
Karabük University, Faculty of Technical Education, Karabük, Turkey, egedik@karabuk.edu.tr
b
Karabük University, Vocational School of Karabük, Karabük, Turkey, mkayfeci@karabuk.edu.tr
c
Afyon Kocatepe University, Faculty of Technical Education, Afyon, Turkey, akecebas1980@hotmail.com
d
Karabük University, Faculty of Technical Education, Karabük, Turkey, hkurt@karabuk.edu.tr

Abstract environmental friendliness with respect to the conventional


gas refrigerators, is becoming a promising technology to
In this study as a new refrigeration technology interested replace the conventional technique [2].
and Magnetic Refrigeration based on the magneto-caloric
effect (MCE) has become a promising competitive The study of magnetic refrigeration was started with the
technology for the conventional gas- discovery of magnetocaloric effect (MCE) 120 years ago
compression/expansion technique contributed climate [3]. It was first discovered by Warburg in 1881. In1890
change occured negative environmental effect due to Tesla [4] and in 1892 Edison independently and
increasing energy consumption is invastigated. Magnetic unsuccessfully tried to benefit from this effect by running
Referigeration is a refrigeration type based on heat engines. In1918 Weissand Piccard explained the
magnetocaloric effect (MCE). It is well know Gd element is magnetocaloric effect. Later Debye and Giauque proposed
a magnetic materials given the best magnetocaloric effect a method of magnetic refrigeration for low-temperature
and Gd5Si2Ge2, MnAs1_xSbx, (Mn,Fe)2 (P,As), physics in order to obtain sub-Kelvin temperatures. In1933
andLa(Fe,Si)13 compounds have been used magnetic Giauque and MacDougall successfully verified the method
materials on magnetic refrigeration technology. It is by experiment. Then it has been used in cryogenic
possible to make refrigeration under 1K temparatures with refrigeration since 1930s. It is maturely used in liquefaction
the magnetic refrigeration and liquefaction of hydrogen and of hydrogen and helium. In 1976, at Lewis Research
helium. Recently, there have been two breakthroughs in Center of American National Aeronautics and Space
magnetic-refrigeration researchs: one is that the magnetic Administration, Brown first applied the magnetic
refrigerators on near room temperature,; the other one is refrigeration in a room-temperature range [5].
that to discover a new magnetic materials for room-
temperature applications. The new materials are The first ‘‘room temperature magnetic refrigerator’’
manganese–iron–phosphorus and arsenic (MnFe(P,As)) containing permanent magnets was designed and built in
alloys. Nowadays rotory and reciprocating type magnetic 2001 in the USA by the Astronautics Corporation [6]. The
refrigerators are exist and studies is going on for the early prototypes were able to reach high magnetic flux
developments of this refrigeraors. densities in the magnetocaloric material only if
superconducting magnets were applied. Research today is
Keywords: Magmetic refrigeration, magnetocaloric effect, focused on improvements of magnetocaloric materials,
magnetic materials magnets and an optimal design of magnetic refrigerator
devices for room temparature applications [7].
1. Introduction
In this study, the concept of magnetocaloric effect is
explained. The development of the magnetic material,
Refrigeration is the process of removing heat from matter
magnetic refrigeration cycles, magnetic field and the
which may be a solid, a liquid, or a gas. Removing heat
refrigerator of room temperature magnetic refrigeration is
from the matter cools it, or lowers its temperature. In the
introduced. Finally some typical room temperature
mechanical refrigeration a refrigerant is a substance
capable of transferring heat that it absorbs at low magnetic refrigeration prototypes are reviewed and
showed the best magnetocaloric effect materials are
temperatures and pressures to a condensing medium; in
presented and some important points for room
the region of transfer, the refrigerant is at higher
temparature applications of magnetic refrigeration
temperatures and pressures. By means of expansion,
technologies are given.
compression, and a cooling medium, such as air or water,
the refrigerant removes heat from a substance and
transfers it to the cooling medium [1]. 2. Magnetocaloric effect

It is well known that the efficiency of the conventional gas- Warburg first discovered the thermal effect of metal iron
compression/expansion refrigeration system cannot when applying it in a varying magnetic field in 1881. Debye
significantly be improved. Also, for the conventional and Giauque explained the nature of MCE later and
refrigeration system, there exist serious concerns for the suggested achieving an ultra-low temperature by adiabatic
environment. Thus, it is necessary and important to demagnetization cooling. In recent years, magnetic
explore other alternative cooling technologies. The refrigeration on the basis of MCE has been greatly
magnetic refrigerator, which has advantages in developed in the room temperature range [5].
refrigeration efficiency, reliability, low noise and

© IATS’09, Karabük University, Karabük, Turkey


Gedik, E. Kayfeci, M. Keçebaş, A. ve Kurt, H.

Magnetic refrigeration relies upon the reversible magnetocaloric effect is modest even near the transition
temperature change some materials exhibit when exposed temperature. Near room temperatures, a material with an
to a changing magnetic field the magnetocaloric effect adiabatic temperature change larger than 2 K/Tesla is
(MCE.) In these materials, a significant change in entropy unusual. For example, a sample of gadolinium near room
can be effected by the application or removal of a temperature will exhibit a temperature change of
magnetic field, and an adiabatic field change is analogous approximately 10 K with the application of a 5 Tesla
to an adiabatic pressure change on a gas. By varying the magnetic field. Gadolinium is considered one of the best-
magnetic field, work is performed and the internal energy known magnetocaloric materials. Until recently, because
of the system changes. Thus, a differential variation in the MCE increases with field strength, superconducting
internal energy can be accomplished by a magnetic work magnets were used almost exclusively in MR devices.
interaction given by the product of the applied magnetic Figure 1 shows experimental data for Gd with a field
field, H, and the variation in magnetization, m [9] change from 0 to 2 Tesla [8].

δw m = Hdm (1) When a magnetocaloric material is subjected to a strong


magnetic field (measured in Tesla, T), the electron spins
Sometimes the magnetocaloric effect is indirectly reported within the material are forced into alignment with the
by isothermal magnetic entropy changes. Researchers can magnetic field. That is, the magnetic field does work to
determine the magnetic entropy change from align the electron spins into what is, thermodynamically, a
magnetization measurements and, using Maxwell’s more highly ordered, lower energy state. The energy
relations for exact differentials of thermodynamic released during this process causes the temperature of the
properties, estimate the magnetocaloric effect. For a material to rise. When the magnetic field is lowered, the
material that has a simple magnetic work mode, the total electron spins return to their more random, higher energy
entropy can be written as a function of temperature, T, state, absorbing heat from the material and causing the
s=s(T,H). A differential change in entropy can be written, temperature to fall. Figure 1 gives an example of the
magnitude of this effect with Gadolinium, a rare-earth
material that exhibits a strong effect and has a Curie
 ∂s   ds  temperature near typical room temperatures. Up to at least
ds =   dT +   dH (2)
 ∂T  H  dH  T moderately strong magnetic fields, the magnetocaloric
temperature increases linearly with the strength of the
applied magnetic field. In addition to Gadolinium, other
where s is the entropy per unit mass. Using the definition
materials exhibiting this effect (including Gadolinium
of heat capacity, the above can be rewritten as, [9]
alloys) have been discovered with Curie temperatures
c H (T, H )  ∂s  (3) covering the range of temperatures usually associated with
ds(T, H) = dT +   dH
T  ∂H  T conventional refrigeration and space cooling applications
[10].
If an isentropic field change is produced, the temperature
change is, [9]

T  ∂s  (4)
dT = −   dH
c H (T, H )  ∂H  T

and using Maxwell’s relations for the equivalence of the


second derivatives, the partial derivative in parentheses
can be replaced to give, [9]

T  ∂m(T, H )  (5)
dT = −   dH
c H (T, H )  ∂T  H

From this simple explanation, one can deduce that a


material with no significant work modes other than
magnetic should have a high ratio of magnetic entropy
change to total entropy to produce a large adiabatic
temperature change. The MCE for a change in magnetic Figure 1. Magnetocaloric effect with gadolinium [10].
field from 0 to H is related to Eqn. (5) by, [9]
In Figure 1, the maximum temperature change induced by
H T  ∂m(T, H )  a 2 T magnetic field is only 5°C (9°F). Stronger magnetic fi
MCE = − ∫   dH (6)
0 c H (T, H )  ∂T  H elds induce a larger temperature change, at 10 T, the
maximum temperature change equals approximately 25°C.
This level of magnetic field strength is, however, only
In contemporary materials, the magnetocaloric effect is a obtained in superconducting electromagnets (such as
strong non-linear function of temperature. In addition, it is a those used in magnetic resonant imaging [MRI] systems).
function of the magnitude of the field change and the initial For a practical, efficient magnetic refrigeration cycle, the
field strength. For most magnetic materials, the cycle needs to operate with magnetic field strengths that
Gedik, E. Kayfeci, M. Keçebaş, A. ve Kurt, H.

attainable by permanent magnets that provide the expansion of the gas, and injection of heat. The two
magnetic field without parasitic energy consumption. As process steps extraction of heat and expansion are
the best high energy permanent magnets can provide fi responsible for a cooling process in two steps. The main
elds in the range of 1 to 2 T, achieving the temperature lifts cooling usually occurs through the expansion of the gas.
needed for air conditioning and refrigeration requires the
use of a regenerative cycle. In essence, the sensible heat The steps of a magnetic refrigeration process are
cycling of the magnetocaloric material needs be provided analogous. By comparing a with b, in Figure.2 one can see
by regenerative heat transfer and the magnetic field- that instead of compression of a gas, a magnetocaloric
induced temperature changes are used to remove heat material is moved into a magnetic field and that instead of
from the cooling load and reject heat to the heat sink [10]. expansion it is moved out of the field. As explained in the
previous section, these processes change the temperature
3. Magnetic refrigeration of the material and heat may be extracted, respectively
injected just as in the conventional process. There are
Magnetic refrigeration is based on a fundamental some differences between the two processes. The heat
thermodynamic property of magnetic materials: the so- injection and rejection in a gaseous refrigerant is a rather
called magnetocaloric effect, which causes a temperature fast process, because turbulent motion transports heat
change if the material is subject to an applied magnetic very fast. Unfortunately, this is not the case in the solid
field under adiabatic conditions. magnetocaloric materials. Here, the transport mechanism
for heat is slow molecular diffusion. Therefore, at present fi
The magnetocaloric effect was discovered in 1881 in iron ligree porous structures are considered to be the best
by the German physicist Emil Warburg. Usually the solution to overcome this problem. The small distances
temperature increases when the field is applied and from the central regions of the material to an adjacent fluid
decreases when the field is removed and the process is domain, where a heat transport fluid captures the heat and
reversible. transports it out of the material, are ideal to make the
magnetic cooling process faster. Furthermore, the not very
Magnetic refrigeration has been recognized as being an large adiabatic temperature differences of magnetocaloric
alternative technology to the conventional vapor- materials will require more often a design of cascade or
compression technology [11-12-13-14]. regenerative magnetic refrigerators than in conventional
refrigerators and hence require additional heat transfer
The reason for this is its comparatively high efficiency and steps. In the Figure.2 (a) is the conventional gas-
the fact that it is an environmentally friendly cooling compression process is driven by continuously repeating
techniques, avoiding ozone-depleting or global-warming the four different basic processes shown and (b) is the
gases. In practice, magnetic refrigeration requires the magnetic refrigeration cycle comparison. Compression is
combination of a magnetic field source with high strength replaced by adiabatic magnetization and expansion by
and a material with a sufficiently high magnetocaloric effect adiabatic demagnetization.
[15].

It is seen that obviously the efficiency of the room


temperature magnetic refrigeration depends strongly on
two essential points: a material with the large MCE and
high magnetic field created by magnetic field source.

In recent years, magnetic refrigeration based on the


magnetocaloric effect has attracted attention as a
candidate technology for minimizing impact to the Earth
environment and minimizing global warming. A key
advantage of magnetic refrigeration is that it does not use
chlorofluorocarbons that can negatively influence ozone
layer depletion.

Operation near room temperature places new demands on


magnetic refrigeration that may be fulfilled by the Active
Magnetic Refrigerator (AMR) cycle, as this cycle is
expected to be able to expand the working temperature
region from low temperature to room temperature. Over
the past few years there have been many studies of
magnetic refrigeration using superconducting magnets or
permanent magnets in the AMR cycle in the room
temperature region.[16–17–18] (a) (b)

3.1. Magnetic Refrigeration Cycle Figure 2. Refrigeration cycles for conventional gas-
compression and magnetic refrigeration [19–
In Figure 2 the four basic steps of a conventional gas- 20].
compression/expansion refrigeration process are shown.
These are a compression of a gas, extraction of heat, 3.2. Advantages and drawbacks
Gedik, E. Kayfeci, M. Keçebaş, A. ve Kurt, H.

The potential advantages of magnetic refrigeration • amorphous fine met-type alloys (very recent) [19].
are valid in comparison with the direct evaporation
refrigerating machines: 4.1. Gd and its alloys

 “green” technology, no use of conventional refrigerants Gadolinium, a rare-earth metal, exhibits one of the largest
known magnetocaloric effects. It was used as the
 noiseless technology (no compressor). This is an refrigerant for many of the early magnetic refrigeration
advantage in certain contexts such as medical designs. The problem with using pure gadolinium as the
applications refrigerant material is that it does not exhibit a strong
magnetocaloric effect at room temperature. More recently,
 higher energy effi ciency. Thermodynamic cycles close however, it has been discovered that arc-melted alloys of
to Carnot process are possible due to the reversibility gadolinium, silicon, and germanium are more efficient at
of the MCE room temperature.

 simple design of machines, e.g. rotary porous heat The prototype magnetic material available for room
exchanger refrigerator temperature magnetic refrigeration is the lanthanide metal
gadolinium (Gd). At the Curie temperature of 294 K, Gd
 low maintenance costs undergoes a second-order paramagnetic - ferromagnetic
phase transition. The MCE and the heat capacity of Gd
 low (atmospheric) pressure. This is an advantage in have been studied in many research activities. [5,21–23]
certain applications such as in air-conditioning and
refrigeration units in automobiles. Table 1. presents the magnetic entropy of some magnetic
materials in the range of near room temperature, from
On the other hand, some disadvantages include: which it can be seen that ∆SM of the GdSiGe alloys are all
considerably large in the presence of a 5 T magnetic field
 GMCE materials need to be developed to allow higher and most of those Curie temperatures are in the room
frequencies of rectilinear and rotary magnetic temperature range. Therefore, this series of alloys meet
refrigerators the requirements of room temperature magnetic
refrigeration. However, many urgent problems such as
 protection of electronic components from magnetic fi easy oxidation, hard preparation, and high price, need to
elds. But notice that they are static, of short range and be settled before they are applied in room temperature
may be shielded magnetic refrigeration.
 permanent magnets have limited fi eld strength. Electro
magnets and superconducting magnets are (too) Table 1. Magetic entropy change some near room
expensive temparature magnetic materials [5]

 temperature changes are limited. Multi-stage machines


lose effi ciency through the heat transfer between the
stages

 moving machines need high precision to avoid


magnetic fi eld reduction due to gaps between the
magnets and the magnetocaloric material [19–20].

4. Magnetic materials for magnetic refrigeration

Since Brown first applied ferromagnetic material


gadolinium (Gd) in the room temperature magnetic
refrigerator in 1976, the research range for magnetic
refrigeration working materials has been greatly expanded.
At first, some ferromagnets concerning the second order
transition were investigated for the large MCE existing in
them. Recently the magnetic materials undergoing a first-
order magnetic transition become the focus after the giant
MCE was found in GdSiGe alloys. Some magnetic
materials that are promise to be used in the future, the Table.2 present the basic parameters for magnetocaloric
following list of promising categories of magnetocaloric
effect of some rare-earth elements, where gj is the g-
materials for application in magnetic refrigerators:
factor of the atom, j is the total angular momentum
• binary and ternary intermetallic compounds quantum number, for the determine of the magnetic
• gadolinium-silicon-germanium compounds moment of an atom. TC is the Curietemperature of
• manganites element, TN and TD are the Neel and Debye
• lanthanum-iron based compounds temperature of this rare-earth elements as shown
• manganese-antimony arsenide Table.2. Table.3 present of the Advantages and
• iron-manganese-arsenic phosphides
Gedik, E. Kayfeci, M. Keçebaş, A. ve Kurt, H.

disadvantages of various near room temparature magnetic This study indicated that magnetic refrigeration could be
refrigerant materials. competitive with conventional gas compression
refrigerators operating below ambient temperatures, with a
Table.2 Parameters of rare-earth elements used in five-year payback for large scale building air conditioning
theoretical MFA calculaions by Tishin [24] or supermarket chillers or food processing plants
(refrigeration and freezing). The energy savings by
replacing a conventional gas-cycle (Freon or ammonia)
refrigeration unit with a magnetic refrigerator were
estimated to be 30% along with the elimination of Freon or
ammonia, as an added environmental benefit Work on the
magnetic refrigeration device a rotary, room temperature,
permanent magnet, magnetic refrigerator began in 1998 at
Astronautics Corporation of America (ACA). In the
meanwhile Ames Laboratory (AL) entered into a three year
with ACA to assist ACA to bring this apparatus, called a
laboratory demonstration magnetic refrigerator (see Fig.
4.2. Perovskite and perovskite-like compounds 3),

Large magnetic entropy change has been found in the In Figure 3 with a custom designed permanent magnet it
perovskite manganese oxides in recent years, so that can produce a magnetic field strength nearly twice as high
these materials attract more and more attention. The main as the general permanent magnet field. A powder of
advantages of this series of compounds over Gd and element Gd is stuffed in pockets inside the ring-shape
GdSiGe alloys are low cost, non-active chemical property regenerator. The regenerator, roughly the diameter of a
(no oxidation), little coercive force as well as high electric compact disk, rotates powdered magnetic material in and
resistance. out of a gap in the powerful magnet at rear [5].

Many studies on these compounds are led mainly in


China, Spain and United States [5]. From Table 1, it is
clear that their Curie temperature also can be easily tuned
to the needed range by introducing some kinds of metal
additions.

However, ∆SM will decrease much in the meantime,


lowering their practicability. For instance, ∆SM of
La0.8Ca0.2MnO3 in the presence of 1.5 T magnetic field
reaches 5.5 J/kg K, about 1.5 times of Gd, but its Curie
temperature is only 230 K. After adjusting Ca ratio to
La0.6Ca0.4MnO3, its Curie point increases to 263 K but ∆SM
decreases to 70% of Gd at 3 T. To improve the Curie
temperatures by adding Sr and Pb, the Curie temperatures
reach 327 and 296 K, however ∆SM decreases obviously.
In addition, the behavior of heat transfer of these Figure 3. Astronautics Corporation of America laboratory
compounds is incompetent because they are oxides [5]. prototype permanent magnet, rotating bed
magnetic refrigerator (a) schematic and (b)
Table.3 Advantages and disadvantages of various near photograph [25–28].
room temparature magnetic refrigerant materials
[25] Some recent research has focused on the use of the
process to perform refrigeration near "room temperature".
Constructed examples of room temperature magnetic
refrigerators are listed in the Table.4 below:

Table 4. Room temparature magnetic refrigerators


between 1998-2007 years [25]

5. Magnetic refrigerators
Gedik, E. Kayfeci, M. Keçebaş, A. ve Kurt, H.

6. Conclusion At the end of this study we can say;

The number of research papers puplished annually over  Large MCE of magnetic material is invastigated
the past 80 years containing the word ‘magnetocaloric’ in for room temparature magnetic cooling
the title abstract, or among the keywords. The values for application
2007 (triangle) are based on the number of papers  Strong magnetic field is required
abstracted during the first three-fourths of the year.
Furthermore while Figure.4 shows that the importance of .
magnetocaloric effect for magnetic refrigeration year after  Magnetic materials available for room
year Figure.5 shows that the number of near room temperature magnetic refrigeration are mainly Gd,
temparature magnetic refrigerators reported per decade GdSiGe alloys, MnAs-like materials, perovskite-
since 1970. like materials,

If we say future perspectives of room temperature  Materials under development for room
magnetic Refrigeration; It can be seen from the earlier temparature magnetic refrigeration are La(FexSi1-
description that main progresses have been made in x)13 and La(Fe0.88Si0.12)13Hy
America. However, with the continual phasic progresses of
room temperature magnetic refrigeration, the whole world  Excellent behavior of regeneration and heat
has accelerated in the research. transfer is required

Nevertheless, it is notable that main work is concentrated  Room temperature magnetic refrigeration is a
on investigations of magnetic materials, lack of new highly efficient
experimental explorations of magnetic refrigerator. From
the former results achieved by researchers, it can be seen  It can be use household refrigerator, central
that there is still a great performance difference between cooling systems, room air conditioners and
magnetic refrigerator and vapor compression refrigerator in supermarket refrigeration applications,
terms of cooling capacity and temperature span.
 It is environmentally protective technology

 This technology must be universalized worldwide

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