Journal of Magnetism and Magnetic Materials 111 (1992)29-33

North-Holland

Magnetocaloric effect in superparamagnets

R.D. McMichael +, R.D. Shull, L.J. Swartzendruber, L.H. Bennett
National Institute of Standards and Technology, Gaithersburg, MD 20899, USA

and

R.E. Watson *
Brookhaven National Laboratory, Upton, NY 11973, USA

Received 22 August 1991; in revised form 2 December 1991

The magnetocaloric effect is calculated for superparamagnetic materials as a function of temperature, field and cluster
size. Assuming classical behavior, a universal curve is calculated from which an optimum cluster moment may be found for
maximum entropy change upon application of a given field H at a given temperature T. Quantum effects are shown to be
small for temperatures above 10 K and fields less than a few tesla. A comparison with results for a spin -7 paramagnet such
as GdaGasOx2 (GGG) is made, which indicates that superparamagnetic materials such as magnetic nanocompositeo -ffer
the possibility of extending the upper useful temperature limit of paramag~etic materials for magnetic refrigeration.

I. Introduction use cf Dy3AIsO12 [4]. For higher operating tem-

In recent years, there has been increasing in-
terest shown in the magnetocaloric properties of
materials for use in magnetic refrigerators [1,2],
especially for cryogenic refrigerators for use-in
specialized aerospace applications, although heat
pumps for use near room temperature have been
constructed as well [3]. For refrigerators operat-
ing in the temperature range between 1.5 and 20
K, the refrigerant material of choice has been
almost exclusively Gd3GasOlz (GGG), although
the upper temperature limit of paramagnetic re-
frigerants has been increased somewhat by the
Correspondence to: Dr. R.D. McMichael NIST, Bldg. 223,
Rm B152, Gaithersburg, MD 20899, USA.
+ National Research Council Postdoctor~d Research Associ-
ate.
* Supported by the Division of Materials S,.iences, US DOE
under contract DE-AC02-76CH00016.
peratures, the magnetocaloric properties of ferro-
magpeti2 materials have been studied for use
with the operating temperature at or near the
Curie point of the material [5-9].
The magnetocaloric effect is the adiabatic tem-
perature change of a material upon application of
a magnetic field. It is Very closely related to the
isothermal field induced entropy change which,
for small temperature changes, differs from the
magnetocaloric effect by a factor of the tempera-
ture divided by the specific heat of the material.
By grouping spins together in superparamagnetic
clusters, the magnetic moments are more easily
aligned than in paramagnetic systems, and for
certain ranges of field, temperature and cluster
size, the entropy of the spins is more easily
changed by application of a field [10]. In this
paper, we calculate the magnetocaloric effect for
the entire range of parameters, demonstrating
how grouting atoms in superparamagnetic clus-

0304-8853/92/$05.00 © 1992 - Elsevier Science Publishers B.V. All rights reserved

30 R.D. McMichael et al. / Magnetocaloric effect in superparamagnets

ters can produce larger entropy changes than in where k is Boltzmann's constant. The magnetic
atomic paramagnets. An optimum cluster size is entropy S c of the sytem can then be found from
determined for a given temperature and applied the thermodynamic relation
field.
The entropy change of a magnetic system can o( :r In z)
be calculated from the thermodynamic Maxwell Sc = - i)T
equation,

(0s) -- , (1)
--Nk [ l n ( 4 r r ) + In (sinh ( __~_
)/(mH --~mH))

T "~ Ii
+l-~coth --~ . (5)
or, integrating over the field,

This expression for the entropy of the magnetic

= dH. (2) moments has a value of Nkln(4~-) at H - 0,
tt
which is analogous to tne quantum-mechanical
As long as the magnetic equation of state, expression, Nk!n(2J + 1), for N moments of an-
M(H, T), is known, the magnetic entropy change gular momentum J. The limit of high H and low
can be calculated. T is S c = Nk[ln(4rr) + 1 - ln(2mH/kT)] which
A sum rule can be derived from eq. (2) con- becomes negative for large H and low T. This
cerning the area under a plot of AS vs T for a anomaly is due to the classical nature of the
given applied field, H. system and is related to the fact that in the
classical system there is no minimum energy scale
comparable to gl.tBH in the quantum system
oO

fo AS dT= -HM o. (3)

where g is the gyromagnetic ratio and /.t B is the
Bohr magneton.
This sum rule implies that for materials with the By increasing the field from 0 to H, the en-
same saturation magnetic moment, M0, those with tropy changes by
high entropy change at a given temperature will
have low entropy changes at other temperatures, ASc = S ( H ) -S(0)
and those materials which do not have a large
entropy change at any particular temperature can = Nk 1 k r coth ~
undergo a moderate entropy change over a
broader temperature range.
+ In (sinh[ mH mH (6)
t t
2,7 Classical superparamagnetic case or, in terms of the unitless variable x = mH/kT,
the entropy change can be written as
In order to avoid the integration specified in
eq. (2), the magnetic entropy of N independent T sc 1[ =- 1-xcoth x+ln
(sinhxtl
- . (7)
magnetic moments m, in a field H, at tempera- M 0H x L x ,a
ture T, is calculated directly through the partition
fucntion Z, assuming classical behavior of the A plot of this function gives the universal curve
moments: and is shown in fig. 1. This curve has a maximum
at

mH
t mH -k--T- ' (4) x= kT = 3.5, (S)
 R.D. McMichael et al. / Magnetocaloric effect in superparamagnets 31

0.28 saturation effects wi!i occur at higher tempera-

tures and lower field, eq. (9) shows that AS in the
0.24
optimized superparamagnetic material is propor-
0.20' tional to H / T .
: ~ 0.16

~ 0.12 3. Quantum superparamagnetic cas,

0.08
Because of the anomalous behavior of the
0.04 entropy of classical magnetic moments in large
fields at low temperatures, it is useful to compare
0
0 ' a ' ,i ' 6 ' a ' 10 the classical results with quantum-mechanical re-
mH/kT sults. The entropy of a collection of spinal parti-
Fig. 1. Entropy change AS of a superparamagnet with satura-
cles is given by
tion moment M 0 as a function of particle moment m, induced
by removal of a field H at a temperature T. For a given value I (J+ ½)gl.LBH (J+½)gl~B H
of H and T, the maximum entropy change occurs at m H / k T coth
= 3.5 where TAS = 0.272MoH.
S O = Nk - kT kT
gi~BH gP~BH
+ coth
where the entropy change is given by
Moll
AS c --- - 0 . 2 7 2 - - - - ~ (9)
2kT

+ In sinh
(i 2kT
(J+2)g#a H )
kT
for constant values of M 0, H and T.
The broadness of the maximum in eq. (7) - In sinh ( g/.t2kTB
H ) (ll)

shows that the entropy change for superparamag-

netic particles drops off slowly as particle sizes
deviate from optimum. This has importance in
that, in any real system, there will be a distribu-
tion of particle sizes, but the performance of the
material will not be drastically degraded by a
particle size distribuAon. The decrease in AS c is
due to a decreasing number of clusters as the
cluster size grows.
In the low field limit, m H / k T << 1, eq. (6)
reduces to
-Nm2H 2 -mMoH 2
= (10)
AS C = 6kT 2 6kT 2
At H = 0, this expression, reduces to the familiar
result S(H = O) = Nk ln(2J + l) and upon appli-
cation of a small field, the entropy changes by
Ng21J,2BJ(J+ 1 ) H 2
ASo= - 6kT2 (12)
To compare the entropy changes described by the
classical and quantum forms, the quantity
gE/.LEJ(J + 1) is identified as m 2, and in the case
of large J, m = gl~B(J + ½). Taking the difference
between the classical and quantum entropy
changes, it is found that

Note that in this limit, AS c increases linearly g/zaH gp.aH

AS o - AS c = Nk 1 -, ,------~c o t h . , ,-----~
with m when the saturation magnetization M 0 is L /-,~1 ,~ ~.. 1
held constant. For paramagnets with magnetic
moments consisting of single atoms, eq. (10) is a
good approximation except for very low tempera-
tures and very high fields, where saturation ef-
fects can be seen. In the low field limit, the
entropy change is proportional to H Z/T 2. In which is the clas~tcal expression for the eatropy
contrast, in a superparamagnetic material where clmnge of a spin-5i paramagnet, which will be
32
1.0
! • spin 7/2 atoms
0.8
',, ...... 10 atom clusters
[... ", ............30 atom clusters
o 0.6 :,...",-..... 100 atom clusters
,E
~,.~--0.4
.-._ ~i -'~'~'':'
o.2
i ,
o 2'0
Fig. 2. Entropy change of a system of spin -7 Gd atoms
induced by removal of a 1 T field for individual spins (GGG)
and clusters of 10, 30 and 100 spins. The 10 atom clusters
have the optimum size at 15.3 K, and the 30 atom clusters
have the optimum size at 46 K.
small for temperatures above 10 K and fields less
than a few Tesla.
A comparison of entropy changes for different
arrangements of Gd atoms under a field of 1 T
calculated using the quantum mechanical expres-
sion is shown in fig. 2. At low temperatures, the
larger cluster moments are nearly aligned and the
entropy change is larger for the more numerous
and smaller atomic moments. At higher tempera-
tures, the larger clusters show the higher entropy
change, with decreased entropy changes at low
temperatures in accordance with the sum rule
given in eq. (3).
4, Conclusions
The main result of these calculations is that
nanocomposite superparamagnetic m,terials have
the potential to exceed the performm~ce of GGG,
the most commonly used refrigerant in cryogenic
magnetic refrigeration, especially when using low
JL"; ~ 1 ..,,! _ _,tA. _ ? I_1
t~c~u:s attmnaole with permanent magnets. Poten-
tial problems facing technical ~pplication of this
class of materials include a reduction in the
zero-field entropy resulting from anisotropy of
the superparamagnetic particles at low T. The
temperature at which such zero-field entropy re-
duction becomes important can be estimated from
R.D. McMichael et al. / Magnetocaloric ef,t%:t in superparamagnets
the peak in the heat capacity of superparamag-
netic particles [11] located near kBT/KV=0.5,
where K is the anisotropy constant and V is the
volume of the particle. The superparamagnetic
blocking temperature is lower, at k BT/KV = 0.04.
Assuming an anisotropy field of 0.1 T, kBT/KV
= 1 at 50 K for the 100 Gd atom clusters, sug-
gesting that the effects of anisotropy on zero-field
"''~'v-o~,~ " ' ..... entropy will only be important below ~ 30 K,
given the assumed cluster size and anisotropy
, , , field.
4'o 6'o 8'o oo Dilution of the magnetic species by a non-mag-
i"ernp (K)
netic matrix material will, of course, reduce the
entropy change per unit mass or per unit volume.
The degree to which this dilution effect can be
minimized by using low volume fractions of host
material depends strongly on the materials se-
lected and on the processing, but in certain cases
superparamagnetic behavior has been observed
with less than 10% host material [12]. By keeping
the volume fraction of the host material iow,
however, interactions between the particles can
become important, and this area is currently be-
ing pursued.
It may be possible to overcome the potential
problems mentioned above because the entropy
change for an optimized superparamagnet is pro-
portienal to H/T rather than H Z / T 2. This may
make it possible to produce large entropy changes
at higher temperatures, or to produce equivalent
entropy changes with reduced fields. In addition,
by regulating the particle size, the entropy change
at a given temperature for a given applied field
can be maximized, with performance falling off
only slowly as particle sizes deviate from the
optimum. This capability for tuning the material
could prove to be very useful for refrigeration
applications.
lilt1.. It II..It I,,.IUl I ~ If..¢.'J
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