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A Peltier cell calorimeter for the direct

measurement of the isothermal entropy change
in magnetic materials
ARTICLE in REVIEW OF SCIENTIFIC INSTRUMENTS JULY 2008
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REVIEW OF SCIENTIFIC INSTRUMENTS 79, 063907 2008

A Peltier cell calorimeter for the direct measurement of the isothermal

entropy change in magnetic materials
Vittorio Basso,a Michaela Kpferling, Carlo P. Sasso, and Laura Giudicib
Istituto Nazionale di Ricerca Metrologica, Strada delle Cacce 91, 10135 Torino, Italy

Received 21 December 2007; accepted 18 May 2008; published online 19 June 2008
We developed a calorimetric technique to measure the isothermal magnetocaloric entropy change.
The method consists in the use of Peltier cells as heat flow sensor and heat pump at the same time.
In this paper, we describe the setup, the constitutive equations of the Peltier cell as sensor and
actuator, and the calibration procedure. The Peltier heat is used to keep the sample isothermal when
magnetic field is changed. The temperature difference between the sample and the thermal reservoir
is kept by a digital control within 5 mK for a magnetic field rate of 20 mT s1. The heat flux
sensitivity around 1 W. With this method, it is possible to measure the magnetocaloric effect in
magnetic materials by tracing the curves of the exchanged entropy es as a function of the magnetic
field H. The method proves to be, in particular, suitable to reveal the role of the entropy production
is, which is connected with hysteresis. Measurement examples are shown for Gd, BaFe12O19
ferrite, and GdSiGe. 2008 American Institute of Physics. DOI: 10.1063/1.2940218

I. INTRODUCTION

Ferromagnetic materials are not in thermodynamic equilibrium because of the presence of hysteresis in their constitutive relationship. The entropy change S = eS + iS is due
both to the entropy exchanged with the surroundings eS and
to the entropy production iS connected with the dissipation
due to hysteresis effect. The thermal properties of a ferromagnetic material are then characterized by an entropy function SH , T, which is a multivalued, hysteretic function of
its variables and by an entropy production term iS 0,
which is a definite positive quantity and a function of the
time history of the variables driving the thermodynamic
transformation.1,2
The experimental determination of the thermal quantities
as a function of magnetic field is becoming more and more
important for applications to magnetic refrigeration around
room temperature.3,4 The development of this cooling technology requires an accurate characterization of the magnetocaloric effect in the room temperature range and at magnetic
field rates comparable to the frequencies of typical refrigeration cycles up to a few hertz. One of the open problems for
the application of magnetic materials to magnetic cooling is
the quantification of the role played by hysteresis and irreversibility effects.5,6 The solution corresponds to the experimental determination of both the entropy change S and the
entropy production iS as a function of magnetic field and
temperature. In the literature, the techniques to characterize
the magnetocaloric effect can be classified on the basis of the
thermal quantity to measure: the isothermal entropy change
S;711 the adiabatic temperature change T;1216 the field
dependence of the specific heat c pH , T.13 However, to
a

Electronic mail: basso@inrim.it.

Also at Politecnico di Torino, Dip. di Fisica, Corso duca degli Abruzzi 24,
10129 Torino, Italy.

0034-6748/2008/796/063907/10/$23.00

characterize materials with irreversibility, one has to measure

directly the heat flux q = TdeS / dt,17,18 a physical quantity
which is directly connected to the entropy rate dS / dt and
to the entropy production rate diS / dt by the expression
q = TdeS / dt = TdS / dt TdiS / dt. The experimental determination of dS / dt and diS / dt is then connected to two capacities
of the instrument: i to keep the temperature of the sample
constant and ii to trace the curves deS / dt as a function of
magnetic field. This provides the possibility to measure the
entropy production term in a closed magnetic field loop with
the expression iS = diS = deS.
In calorimeters that are able to determine the heat flux,
one measures the heat current established between a sample
and an isothermal reservoir isothermal calorimetry1921.
Peltier cells have been shown to be heat flux sensors particularly suited for the measurement of the magnetocaloric effect, because they are highly sensitive, little affected by the
presence of magnetic field, and are available with small time
constants.9,10 However, the current methods Refs. 9 and 10
are based on use of Peltier cells as passive sensors, so they
sense a heat flux when a temperature difference between the
sample Ts and the thermal bath Tb is present. Then, the measurement can be considered isothermal only at very low
magnetic field driving rates. With the motivation to expand
the Peltier cells toward higher field rates, we have developed
the active use of the cells.
The concept consists in using a symmetric arrangement
of two Peltier cells and two copper blocks thermal bath
Ref. 22 and to obtain isothermal condition by the Peltier
heat. Different from previous works in which the Peltier cells
are used for heat compensation only,19,20,2325 our method
consists in using the same cell both as a heat sensor through
the Seebeck effect and actuator through the Peltier effect
and corresponds in this respect to the new class of calorimeters foreseen in Ref. 9. The active measurement is obtained

79, 063907-1

2008 American Institute of Physics

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063907-2

Rev. Sci. Instrum. 79, 063907 2008

Basso et al.

by digital feedback control, driving an electric current i

through the cells while the magnetic field is changed in time.
We realized the setup to work around room temperature
and we performed its calibration in the temperature range of
233 353 K 40 to + 80 C. We tested the method and the
instrument by performing measurements on selected magnetic samples: i Gd, ii BaFe12O19, iii GdSiGe. The
isothermal entropy change was measured on Gd and compared to independent measurements on the same sample giving excellent quantitative agreement. On hard barium ferrite
of composition BaFe12O19, we measured the entropy exchanged along the magnetization curves and we were able to
discriminate the relative contributions of the entropy change
S and entropy production iS in a closed loop. To sustain
our data, we found that, as expected, the energy loss TiS
provided by the calorimeter agrees with the energy loss
given by the magnetic hysteresis loop area. Finally, to test
the possibility of the instrument on materials of interest for
magnetic refrigeration around room temperature, we measured a sample of GdSiGe alloy displaying the so-called
giant magnetocaloric effect GMCE. We are able to plot the
hysteresis curve of the exchanged entropy as a function of
magnetic field. This kind of curves contains the full information on the material for its application as a refrigerant in
cooling machines.
II. Calorimeter
A. Measurement principle

The general scheme of the experiment consists of the

sample, the thermal reservoir, and the Peltier cell, acting as a
sensor and actuator, connecting the two. A change in time of
either the magnetic field, with rate dH / dt, or the temperature, with rate dTs / dt, corresponds to an entropy change S
and an entropy production iS in the sample. The corresponding heat flux is q = TsdeS / dt = TsdS / dt TsdiS / dt. For
the sample, the heat current qs, positive toward the sample, is
qs = Ts

d eS
eS H
eS dTs
= Ts
+ Ts
.
dt
H t
Ts dt

The Peltier cell is, as a passive element, a thermal conductor, and, as actuator, a source of heat current. The heat
flux at the cell in steady state, is governed by the following
equation see Appendix for the derivation:
1
qs = Pi + Ri2 K PTs Tb,
2

where the three terms on the right hand side represents: i

the heat current due to the Peltier effect P is the Peltier
coefficient and i is the electric current passing through the
cell; ii the Joule heating R is the electric resistance of the
cell, and iii the heat conduction current due to the temperature difference across the cell K P is the total thermal
conductance. The factor 1 / 2 in the Joule heating term appears because half of the Joule heating flows to the sample
and half to the bath.
The behavior of the sample is given by equating the two
previous expressions 1 and 2. We obtain a differential
equation for the sample temperature Ts:

FIG. 1. Top Symmetric arrangement of Peltier cells in the calorimeter.

Bottom Electric connection of the cells.

Ts

1
eS dTs
eS H
+ K PTs Tb = Ts
+ Pi + Ri2. 3
2
Ts dt
H t

The right hand side of the equation contains the sources and
sinks of heat. The three terms are the magnetocaloric heat,
the Peltier heat, and the Joule heat. When i = 0, the sensor is
passive and represents a thermal conductor only. The temperature Ts of the sample is then bound to change when the
magnetocaloric heat on the right hand side of the equation
is different from zero. When i 0, the sensor is active and if
the current i is such that the sum of the three terms on the
right hand side is zero the magnetocaloric heat is compensated by the Peltier heat Pi and the Joule heat. If initially
Ts = Tb, the temperature of the sample will not change and
isothermal conditions are obtained.
The heat flux toward the sample qs and the temperature
difference between the cell faces Ts Tb are related to the
electric voltage v and current i through the cell see
Appendix.2 The qs of Eq. 2 is then measurable and its time
integration between starting state 0 at t = t0 with H = H0 and
Ts = Tb, and any state t with H = Ht and Ts = Tb gives
eS =

t0

qs
dt
Ts

as a function of the history of the magnetic field Ht at

constant temperature Ts = Tb.
B. Measurement setup

The calorimetry setup implements the conditions of the

measuring principle by employing a symmetric arrangement
of two identical Peltier cells placed in contact with two parallel faces of the sample see the scheme of Fig. 1a. The
symmetry is chosen because, for the active use of the Peltier
cells, all the heat flux exchanged by the sample has to flow
through the measuring cells. The ensemble is placed in a
tube which is evacuated in order to minimize heat flux losses

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Rev. Sci. Instrum. 79, 063907 2008

Peltier cell calorimeter

given by the constitutive equations of the Peltier cells. The

two equations are derived from the theory of thermoelectric
effects see Appendix under the condition that the sample
and the bath have homogeneous temperatures and the cell
has negligible thermal capacity but finite thermal conductivity. The two equations are
1
v R Pi,
P

1
1
qs = Pi + Ri2 v R Pi,
2
SP

Ts Tb =
FIG. 2. Color online Picture of the calorimeter. Top Brass tube hosting
the calorimeter. Inlet and outlet are for the cooling with nitrogen gas. Center An open calorimeter: to each copper bar a Peltier cell is attached. The
Gd sample is shown above the cell of the lower bar.

from the sample. Both sensor calibration and measurements

are performed at the same vacuum level with pressure of
0.5 Pa obtained by a rotary pump. The Peltier cells are in
thermal opposition and their bath sides are attached to copper
blocks thermal bath. The two blocks have been cut out
from a copper rod of diameter 15 mm and length of 120 mm.
The two Peltier cells are connected electrically in series circuit shown in Fig. 1b. A picture is shown in Fig. 2.
The measurement of the vt and v0t signals is done by
an Agilent E1419A Multifunction programmable board and
the current it is given by it = v0t vt / Rc. A Keithley
nanovoltmeter is used as high sensitivity amplifier for small
vt signals.
The Peltier cells are commercial cells with 60 junctions
on an 8 9.6 mm2 surface, 0.9 mm height Thermion
1MC04-060-02-0000 with a nominal electrical resistance
of 1.51 . These cells were chosen because they have a
fast response time. In the circuit of Fig. 1b, the resistance
Rc = 1 k, much larger than the resistance of the cells, permits one to set the needed current it by setting directly the
voltage v0t = Rcit + vt through the voltage output of the
Agilent E1419A.
The temperature of the copper blocks Tb is regulated by
compensating the heating effect of an electrical heater covering the external part of the blocks and the cooling effect of
the flux of cold nitrogen gas vapors of the liquid in an outer
chamber of the vacuum tube. The temperature of the blocks
Tb is measured by a thermocouple placed in the vicinity of
the Peltier cells. With this method, Tb can be regulated within
an accuracy of 0.01 C over 100 s in the range of 233
353 K 40 to + 80 C.
The magnetic field H is generated by an electromagnet.
The whole calorimeter setup is inserted in the 20 mm gap
formed by two tapered FeCo pole faces of 60 mm diameter.
The magnetic field is measured by a Hall probe placed outside the vacuum tube. The maximum magnetic field intensity
is around 0H = 2.3 T.
The samples must have two flat parallel faces in order to
have a good contact with the measuring cells. Thermal conducting grease is used in order to have a uniform thermal
contact between samples and cells and to decrease the thermal contact resistance.
C. Sensor equations and calibration

The relationship between the measured electric quantities vt and it and the thermal quantities Ts Tb and qs is

where P and P are the effective Seebeck and Peltier coefficients, respectively, R P is a parameter having the dimensions of an electrical resistance and including the true electrical resistance of the cell, S P = P / K P is the sensitivity, and
K P is the total thermal conductance. All these effective coefficients take into account the finite thermal conductivity of
the ceramic plates which are covering the cell, as shown in
Appendix. These equations are appropriate to describe
Peltier cells with fast response time since they do not describe the transient state. The hypotheses of uniform temperature in the sample depends on its thermal diffusivity
and thickness d and has to be checked case by case.
In order to pass from the measured voltage v and current
i to T and qs, the effective parameters of the Peltier cells
S P, R P, P must be calibrated. The two equations 5 and 6
can be directly applied to describe the measuring system
composed of two cells of our setup because the two cells are
in constant contact with the same sample and the same bath.
The effective parameters refer then to a two-cell system.
The calibration is performed by the following three independent experiments.
Determination of S P. i The cells are operated with zero
electric current passive configuration. ii A known
source of heat an electric heater generating a Joule heat
q0 = Rhi2h substitutes the sample. In this case, the heat current qs = q0 is imposed by the heater and the Peltier cell
voltage is proportional to the heat current v = S Pq0 from
Eq. 6 with i = 0. The sensitivity S P = v / q0 is determined
by measuring the Peltier voltage v under steady conditions.
Determination of R P. i The cells are operated in active
configuration i 0. ii Both sample and bath side faces
of the cells are placed in contact with the thermal bath
represented by the two copper blocks. If the blocks have
sufficiently large heat capacity and thermal conductivity,
the two faces of the cells are at the same temperature
T = 0. This isothermal condition is likely to be conserved even when a small electric current i = i0 is supplied
to the cells and a small heat current qs is traversing them.
In Eq. 5, the temperature difference Ts Tb is identically
zero and the parameter R P is determined from Eq. 5
as the ratio between the measured v and the imposed i0:
R P = v / i 0.
Determination of P. i The cells are operated in active
configuration i 0. ii The sample is placed between the
cells. If a continuous heat current is delivered from the
thermal bath to the sample by supplying the cells with a

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Basso et al.

constant electric current i = i0, the temperature of the

sample will increase T 0. The steady condition will
be reached when the heat flowing toward the sample
Pi0 + 1 / 2Ri20, Peltier heat and Joule heat terms of
Eq. 6 is compensated by the heat flowing backward
to the thermal bath 1 / S Pv R Pi0 = K PT, thermal
diffusion term of Eq. 6. This steady condition qs = 0 in
Eq. 6 is well verified if there is negligible heat loss. P
is determined as
P =

1 v
1
R P Ri0 ,
2
S P i0

by setting the constant current i0, measuring the Peltier

voltage v, and using the S P and R P coefficients calibrated
in the previous two experiments.
The effective parameters S P, R P, P of the cells depend
on temperature, while the dependence on the magnetic field
is negligible. The calibration of our setup has been made by
performing the three calibration experiments at selected temperatures of the thermal bath in the range of 233 353 K
40 to + 80 C. S P is determined by using a strain gauge
as electric heater, with a resistance of Rh = 120 , placed
between the cells. The voltage v is measured as a function of
the ih in the range of 5 20 mA and S P is determined by
linear best fit of v as a function of q0 = Rhi2h. The error for
each point of S P is less than 1%. The value of R P is determined by measuring v with i0 in the range of 1 2 mA and
making a linear best fit. Low current values were chosen not
to alter the temperature of the copper blocks. The error for
each point of R P is also less than 1%. By observing the
transient behavior of the voltage vt after a current step, we
observe an exponential approach to stationary value with a
time constant = 0.2 s. This time constant is the limit of the
frequency harmonics that can be observed in a magnetocaloric experiment. By changing the magnetic field over a period around a hundred of seconds, the main frequency is
about two decades below the frequency cut. The possible
influence of the presence of a magnetic field on the Peltier
cell parameters was checked by measuring the value of S P
and R P at constant field of 0H = 2 T. The difference between the values at zero field is below the error of the determination of S P and R P, then the calibration coefficients S P
and R P can be considered functions of temperature and are
well described by the fit reported in Fig. 3. For the determination of P, we measured v under i0 = 1 2 mA and we
computed P by Eq. 7. The sample used for the calibration
of P is a Gd sample Sec. III A.
The calibration as a function of temperature requires a
particular care in the case of heating because one has to
consider possible degradation of properties of the cells. The
nominal maximum operation temperature for the cells is
85 C. We performed several tests for the use of the cells
above room temperature and we found that when the cells
heated below 80 C, the sensitivity S P do not deteriorates.
For our aims, we check the time stability of the cells of the
coefficient by performing the calibration at the room temperature before and after heating to the maximum operation

FIG. 3. Color online Coefficients S P, R P, and P as a function of

the temperature T, obtained from the calibration of the the measuring
Peltier cells Thermion 1MC04-060-02-0000. The curves shown
are S P = 103+ 0.503T T0 3.27 103T T02 2.09 105T T03 8.57
108T T04, R P = 3.77+ 0.02T T0, P = 10.6+ 0.038T T0. With T0
= 296 K .

temperature. For a maximum temperature of 85 C, the values are changing within the error.
Figure 3 reports the results of calibration as a function
of temperature for the cells used in the measurements shown
in this paper. The room temperature T = 296 K values are
S P = 0.103 V / W, R P = 3.77 , P = 10.6 V, the effective Seebeck coefficient, given by P = P / T, where T is the absolute
temperature, is P = 35.8 mV/ K. The electrical resistance of
the series of the two cells is R = 3.01 . The total thermal
conductance of the cells K P, given by K P = P / S P, results
K P = 0.348 W K1.
D. Heat flux measurement and T control

The heat current qs and the temperature difference

Ts Tb are computed from Eqs. 6 and 5, respectively, by
using vt and it signals and the values of the parameters
determined by the calibration. The measured voltage signal
vt includes constant instrument offsets and magnetic field
induced voltage, which are subtracted. The sensitivity of the
instrument as a heat flux sensor depends on the sensitivity of
the measurement of v. At room temperature T = 296 K,
S P = 0.103 V / W by using a nanovoltmeter, we have a resolution around q = 1 W. This limit is mainly due to the electrical noise present. To decrease the noise level, the signals
v0 and v are sampled at t = 1 ms and averaged over a period
ranging from 10 to 100 ms.
In active isothermal measurement, T = Ts Tb is controlled to the reference value Tref = 0 by setting the appropriate current i. Its value is determined by a proportionalintegral digital feedback control: it = k pet + etdt / i
where the error is et = PTref T = v R Pi and the

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Rev. Sci. Instrum. 79, 063907 2008

Peltier cell calorimeter

ery execution step, it computes numerically the current i

to be set, then it applies the corresponding v0 = v + Rci. The
control routine runs at t = 10 100 ms. For the Peltier cells
used in this paper, we have determined as optimal values
k p = 0.8 1 and i = 0.75 s.
In Fig. 4 is shown a comparison of the active and
passive measurements on a Gd sample at room temperature
Tb = 296 K see next section for the details on the sample.
The magnetic field is increased up to the maximum of
0Hmax = 1.5 T, then decreased to zero. The field rate was
0H / t = 20 mT s1. In the passive measurement, the T is
proportional to the heat flux. With the active control, T is
kept very close to zero apart when the heat flux is changing
in time. The peaks are below 3 mK. In the inset of Fig. 4, a
detail of the es as a function of the applied magnetic field H
is shown. The specific entropy es is given by the integral
FIG. 4. Color online Comparison between active and passive measurement. T = Ts Tb is the difference between the temperature of the sample
and that of the bath. The magnetic field is the same of Fig. 5. T = Ts Tb is
computed by the sensor equation Eq. 5 by using the calibration coefficients and the measured vt and it signals. Inset es as a function of
magnetic field for the two measurements.

control system parameters k p and i are set to obtain a fast

approach of the measured PT = v R Pi to zero with a few
oscillations. The control routine is realized digitally on the
Agilent E1419A Multifunction programmable board. At ev-

es =

1
mT

qstdt ,

t0

where m is the sample mass and T = 296 K is the temperature

of the thermal bath. For the Gd sample at T = 296 K, above
its Curie point TC = 293 K, we expect a negligible entropy
production is 0. The measurement gives directly the entropy change in the system s = es as a single valued curve
with no hysteresis.

FIG. 5. Isothermal entropy change measured on a

Gd sample at T = 293 K. H is the applied field waveform
and es is the measured entropy change. v and i
are voltage and current measured at the Peltier cells.
T = Ts Tb and qs are computed by the sensor equations
Eqs. 6 and 5 using the calibration coefficients.

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063907-6

Basso et al.

In the measured passive curve, we observe a hysteresis

effect which is due to the time delays introduced by the fact
that the sample is changing temperature. To evaluate the time
delays introduced, we have to consider Eq. 3. In that equation, the time constant is s = Cs / K P, where Cs = TsdS / dTs is
the thermal capacity of the sample. An estimate of s from
the passive experiment can be obtained by the integration
of Eq. 1. We get S = qs / Tsdt Cs / TsdTs / dtdt.
If the variations of Ts are small with respect to its
value, we can take 1 / Ts outside the integrals: S
= qsdt CsdTs / dtdt / Ts. With constant Cs and by using
qs = K PT, we obtain S = qsdt + sqs / Ts. In the Gd experiments of Fig. 4, the passive curve reduces to a single
valued curve by using the previous approximated formula if
we use a time constant s = 0.8 s.
The curve performed by the active method is much
closer to a single curve because the control system was able
to keep the sample temperature sufficiently close to that of
the bath and provides with sufficient accuracy directly the s
versus H curve. The active method is therefore particularly
useful in experiments in which one needs to obtain the es
versus H curve in a single experimental run.
An example of all the time signals in active measurements is shown in Fig. 5. In the experiment shown, the magnetic field is changed at the constant rate 0H / t
= 20 mT s1. In the active measurement qs, given by Eq. 2,
is mainly due to the Peltier effect. From the case shown in
Fig. 5, it results that the Joule heat contribution is less than
0.01% and the heat conduction term is almost always equal
to zero, except the T peaks where it reaches 10% of the
Peltier heat flux. Positive qs means heat absorbed by the
sample, negative qs means heat released by the sample as it
is expected for Gd, that has a conventional magnetocaloric
effect in which heat is released under an increasing field and
absorbed under decreasing.

Rev. Sci. Instrum. 79, 063907 2008

FIG. 6. Set of curves of entropy change s vs applied magnetic field H at

constant temperature Ts measured on Gd.

240 340 K. In Fig. 6, the exchanged entropy Eq. 8 is

plotted as a function of the applied magnetic field H at selected temperatures above Tc. We verified that the graph
es versus H, obtained by first increasing and then decreasing the magnetic field, describes a single valued curve and
the final value returns to the initial value Fig. 6. The entropy production is found to be negligible is 0 also below
the Curie point of Gd. Then, our measurement gives directly
the entropy change in the system s = es.
In Fig. 7, the s is shown at the selected magnetic field
0H = 0.4, 0.9, and 1.5 T as a function of T = Tb. The values
were extracted from the isothermal curves sT , H. In the
picture, our data are compared to the s measured on a
sample taken from the same sheet with the calorimeter developed at the University of Zaragoza16,27 with good agreement of the two curves.

III. Measurement examples

A. Reversible effect: Gadolinium

Gadolinium is a ferromagnet with a large spontaneous

magnetization at low temperature 0M sT = 4.5 K = 2.7 T
Ref. 26 and a Curie temperature around TC = 293 K. For
this reason, it has been studied intensively as a material for
magnetic refrigeration at room temperature.
The sample is a 5 5 1 mm3 sheet with mass
m = 0.217 g. The sample is sufficiently thin to guarantee
uniform temperature during the experiments. With a thickness d = 1 mm and thermal diffusion coefficient = 3.74
106 m2 s1 for Gd, we obtain a diffusion time
= d / 22 / of about 0.1 s, below the response time of the
measuring cell 0.2 s.
The magnetic field H is applied parallel to the long axis
of the sample. The measurements are performed by i setting the temperature of the thermal bath Tb to a given constant value, ii start the measurement by first increasing the
magnetic field up to the maximum of 0Hmax = 1.5 T, then
decreasing to zero. The measuring cells are operated in active configuration by controlling Ts Tb = 0. The temperature
of the thermal bath Tb was changed in the range of

FIG. 7. Color online Isothermal entropy change in Gd. Full symbols

Entropy change s vs temperature T at several applied magnetic field
values measured on a Gd sample with the calorimeter developed in the
present paper. Open symbols Measurement of a sample taken from same
sheet, performed by the calorimeter developed at the University of Zaragoza
Refs. 16 and 27.

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Rev. Sci. Instrum. 79, 063907 2008

Peltier cell calorimeter

s
PM phase

H=0

H=Hmax

FIG. 8. Curves of the integral of the exchanged heat Tes measured on

isotropic BaFe12O19 as a function of the applied magnetic field H. The
history of the field is full line saturation loop 0, Hmax, +Hmax, Hmax, 0;
dashed lines return branches 0, Hmax, +Hpeak, Hmax, 0. The values are:
0Hmax = 1.8 T and 0Hpeak = 0.3,0.4 T. Inset A magnetic hysteresis loop
for the same material. The measurements are at room temperature
T = 296 K.

FM phase

T
FIG. 9. Illustration of the entropy as a function of temperature for a material
with a magnetic field driven phase transition. There is hysteresis in the s-T
curves. The full arrows trace the temperature and field variation of the
magnetocaloric experiments performed.

B. Irreversible effect: Hard ferrite

Barium ferrite of composition BaFe12O19 is a ferrimagnet with saturation magnetization 0M s = 0.48 T at room
temperature and a Curie temperature around TC = 742 K.28
The magnetocaloric effect is then expected to be much lower
than that of Gd. However, barium ferrite has a large coercive
field due to its high uniaxial magnetic anisotropy anisotropy
field 0HA = 2K1 / M s = 1.7 T. This material was selected in
order to verify the ability of the instrument to measure the
entropy production. By performing a closed hysteresis cycle,
the dissipated energy corresponds to the area of the magnetic
loop: Tis = 0 HdM. The sample is a cylinder with
height h = 1.45 mm, base diameter d = 6.7 mm, and mass
m = 0.246 g of sintered isotropic barium ferrite. A hysteresis
loop of the sample is shown in the inset of Fig. 8.
The calorimetric experiment is realized at room temperature T = 296 K by applying the magnetic field parallel to the
cylinder axis. The field history consists of the following sequence: 0, Hmax, +Hmax, Hmax, 0 with field sweep rate
0H / t = 24 mT s1. The voltage signal vt was amplified
by a Keithley nanovoltmeter with gain G = 10 000. The heat
exchanged is computed by the expression
T s es =

1
V

qstdt ,

t0

where V = 5.1 108 m3 is the sample volume and Ts

= 296 K is the temperature of the sample. The curve is shown
in Fig. 8.
The qualitative interpretation of the shape of the curve of
Fig. 8 is that a reversible magnetocaloric effect close to the
saturation is superimposed to an upper shift of the curve that
occurs each time the field traverses the range around the
coercivity and is connected with the dissipation of energy. A
curve with a similar shape was already seen for Ni see Ref.
1, p. 517. To sustain this interpretation, we have performed

measurements of return branches maximum positive field

0H = 0.3, 0.4 T shown as dashed lines in the picture. Only
a part of the loop is traversed and the dissipation reduces
accordingly, as it can be seen by the different positions of the
reversible branches at high negative fields.
Quantitatively, the calorimetric data give the dissipated
energy in closed hysteresis loop Tis = Tdis = Tdes. For
the saturation cycle, the value is Tis = 0.205 MJ m3. This
value has to be compared to the area of the magnetic saturation hysteresis loop. By using the data shown in the inset of
Fig. 8, the area is 0 HdM = 0.209 MJ m3.
C. Irreversible effect:

GMCE

in GdSiGe

Since the discovery of GdSiGe,29 great attention is

devoted to materials displaying the so-called GMCE in
which a large entropy change is achieved by the magnetic
field, because of the presence of a coupled magnetostructural
phase transformation. The characterization of out-ofequilibrium properties is particularly important here because,
when equilibrium thermodynamics methods are applied to
GMCE materials for the determination of the entropy
change, incongruent results may appear.5,6
The compound Gd5Si2Ge2 displays a coupled magnetostructural first order phase transformation between a low
temperature ferromagnetic FM orthorhombic Gd5Si4-type
structure and a high temperature paramagnetic PM monoclinic Gd5Si2Ge2-type structure30 at T = 288 K. The phase
transformation can be induced by the application of a magnetic field and the entropy as a function of the temperature at
different magnetic fields has the behavior sketched in Fig. 9.
The sample analyzed in this paper is polycrystalline with
nominal composition Gd5Si2.09Ge1.91. It is a piece of thickness 1.4 mm, irregular lateral sizes of about 4.5 4.5 mm
and mass m = 0.149 g. The experiments were performed by

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063907-8

Rev. Sci. Instrum. 79, 063907 2008

Basso et al.

FIG. 10. Exchanged entropy es measured on polycrystalline

Gd5Si2.09Ge1.91 as a function of the temperature T at 0H = 1.5 T.

starting at the temperature T0 = 273 K in which the material

is fully in its FM state, then increasing the temperature of
the bath up to the measuring temperature T = Tb inducing
partially or completely the FM to PM transformation, then
performing the calorimetric experiment at constant Tb. The
magnetic field is applied parallel to the 4.5 4.5 plane.
In Fig. 10 are shown the values of es as a function of
temperature for the maximum field of 1.5 T. For this test, the
magnetic field was increased up to 0H = 1.5 T PM to FM
and decreased down to 0 T FM to PM. After each experiment, the temperature is decreased back to T0 in order to start
from a well defined FM initial state see Fig. 9.
The Gd5SixGe1x4 with 0.503 x 0.575 is known
from the literature30 to form two phase alloys. The primary
phase is the Gd5Si2Ge2-type structure with GMCE effect.
This secondary phase is a Si-rich phase with Gd5Si4-type
structure. It is FM with a Curie point close to room temperature. The behavior of the measured sample can be interpreted
as the superposition of the behavior of these two phases. In
the entropy change of Fig. 10, we observe the GMCE peak at
T = 288 K associated with the behavior of the primary
Gd5Si2Ge2 phase and smaller peak at T = 303 K associated
with the Curie point of the secondary Si-rich phase. The
values obtained for the temperatures are in agreement with
the phase diagram reported in Ref. 30 and the values of the
entropy change are comparable with those obtained on similar samples investigated in Ref. 30.
In Fig. 11 are shown the curves of es as a function of
the magnetic field for two selected temperatures. In the picture, the magnetic field was changed according to the following field history: 0, Hmax, Hmax, +Hmax, 0. The field sweep
rate is 0H / t = 20 mT s1. These curves reveal the superposition of two contributions: one from the entropy change
associated with the latent heat of the first order phase transformation GMCE which is hysteretic and the other with the
conventional magnetocaloric effect of the phases that has no
hysteresis. At T = 288 K, the primary phase Gd5Si2Ge2 of the
sample is already partially transformed in PM and the application of a magnetic field immediately start to transform

FIG. 11. Curves of the integral of the exchanged entropy es measured on

polycrystalline Gd5Si2.09Ge1.91 as a function of the applied magnetic field H.
The history of the field is 0, +Hmax, Hmax, +Hmax, 0, with 0Hmax
= 2.05 T.

back to FM as it can be seen from the presence of hysteresis.

When the phase is transformed back to FM around 1.5 T,
the loop has a saturating shape. The lower slope ds / dH corresponds the conventional magnetocaloric effect of the FM
phase. At T = 296 K, the sample is fully in its PM phase. At
magnetic fields below 1.5 T, we observe the conventional
magnetocaloric effect of the phases. The partial hysteresis
loop seen corresponds to a partial phase transformation to
FM that is completely recovered back when the field is removed. The same phenomenology is observed when the
magnetic field is applied in the opposite direction. A minor
effect that has to be noticed is that the first time that magnetic field is increased, after the sample is heated from fully
FM state, the s versus H branch is found to be slightly
shifted to higher field. This may be due to the fact that the
hysteretic phase transformation softens slightly after the first
cycle. The entropy production is seen as a small positive
shift of the es curves. The value of es after one-half loop
0-Hmax-0 does not return exactly to zero, however, the effect is only around 1% of the maximum entropy change.
IV. CONCLUSIONS

In this paper, we have studied and implemented a technique to measure the isothermal entropy change due to the
magnetic field by employing Peltier cells in active way to
compensate the magnetocaloric heat. The setup has been realized using a symmetric arrangement of two Peltier cells
and the active measurement is obtained by a digital feedback
control. With the active method, the curve es traced while
changing the magnetic field with time at a certain rate has a
strongly reduced dynamic hysteresis with respect to the passive case. After calibration, we tested the setup by measuring
the magnetocaloric effect of three different materials: Gd,
BaFe12O19, and GdSiGe. For Gd, our measurements give
the curves of sH , T as a function of the applied magnetic
field H. Our data agree with independent measurements. The
exchanged entropy es is measured as a function of the magnetic field history. This is the kind of measurement which is

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063907-9

Rev. Sci. Instrum. 79, 063907 2008

Peltier cell calorimeter

sample

2. Thermoelectric equations

Ts
qs

Tj
p

i
Tj

bath

qb

Tb

FIG. 12. Peltier cell connected with the sample and the thermal bath. The
temperatures at junctions T js and T jb can be different from the temperatures
at the sample Ts and bath Tb, respectively, when the heat fluxes qs and qb are
not zero.

of interest for the characterization of materials with the giant

magnetocaloric effect because the effect of hysteresis on the
refrigerant capacity has to be determined. The entropy production in a closed loop is measured on a sample of hard
ferrite and compared to the magnetic hysteresis loop area. A
measurement example is shown for GdSiGe, revealing the
hysteresis of the entropy as a function of the magnetic field.
The setup described in this paper removes the limitations
of the passive method in which time delays are introduced by
the heat capacity of the sample. The time constant is s
= Cs / K P, where Cs is thermal capacity of the sample and K P
is the thermal conductance of the cells. Active and passive
reduce to the same at low driving speed, the active method is
necessary for the cases in which both s is large or when the
magnetic field driving rate cannot be too low. Both cases are
of interest for the characterization of magnetic materials for
magnetic cooling. With the presented active method, we are
still limited by the time constants of the cells related to the
ratio C P / K P, where C P is the thermal capacity of the Peltier
cell. In this work, we have selected proper cells with short
time constants. In future works, we will investigate how to
take into account the dynamic effects in the theoretical description of the measuring cells.
ACKNOWLEDGMENTS

We thank for the samples: A. Kedous Lebouc for the Gd

sheet, F. Fiorillo and C. Beatrice for the hard ferrite, M.
Pasquale, V. Pecharsky, and K. Gschnidner for the GdSi
Ge. We thank the group of Professor Burriel University of
Zaragoza for performing the entropy measurement on a Gd
piece from the same sheet.
APPENDIX: THERMOELECTRIC EFFECTS
IN PELTIER CELLS
1. Peltier cell

A Peltier cell is a thermoelectric device made of junctions of semiconductor pillars, doped p and n, with positive
and negative thermoelectric power respectively Fig. 12.
The pillars are connected electrically in series. For what concerns, the thermal conduction between the planes, the pillars
constitute a parallel thermal circuit.

The thermodynamic forces are the voltage at the terminals v and the temperature difference between the two junctions planes T j = T js T jb, which is taken here to be uniform
on the planes. The currents of interest are the electric current
i and heat current at the interface between the cell and the
sample qs. From the equations of thermoelectric effects2 applied to the geometry of the cell, one has
v = Ri + T js T jb,

A1

1
qs = i + Ri2 KcT js T jb,
2

A2

where is the total Seebeck coefficient of the junctions, R is

the total electric resistance of the pillars, = T is the Peltier
coefficient, T is the absolute temperature, and Kc is the total
thermal conductance of the columns. The three terms of Eq.
A2 represent i the Peltier heat, ii the Joule heat, and iii
the heat flux due to thermal diffusion. The factor 1 / 2 in the
Joule heat term appears because half of the heat is delivered
to the sample side and half to the bath side. The difference
between the heat currents at the sample side qs and at the
bath side qb is the Joule heat:
A3

qs qb = Ri2 .

3. Sensor equations in stationary state

When the cell is in contact with the thermal bath at temperature Tb and the sample at temperature Ts, we have to take
into account the presence of the electrical insulating layers.
These are made of a ceramic material acting also as a thermal insulator. When a heat flux is traversing the layers we
have, because of the heat conduction equation q = KT, a
difference between the temperatures T js Ts at the sample
side and T jb Tb at the bath side. If we suppose that the
temperature in the bath and in the sample is homogeneous
and that the layers are thin enough to consider them as a
body with a negligible thermal capacity, then the two heat
currents qs and qb through the layers are continuous. The
thermal conductivity of the layers is taken as l of area A
and thickness dl / 2 each and the two heat conduction equations give qs = 2KlTs T js and qb = 2KlT jb Tb, where
Kl = lA / dl is the thermal conductance of the two layers 2Kl
is the conductance of each layer. Tb is a constant independent of the heat flux qb. The temperature difference between
the sample and the bath is the sum of the three differences
Ts Tb = Ts T js + T js T jb + T jb Tb. By using the heat
conduction equations for the two layers, we get
Ts Tb = T js T jb

1 qs + qb
.
Kl 2

A4

By substitution of Eqs. A2 and A3, we get the relation

between the two temperature differences:
T js T jb =

KP
K P i
Ts Tb + 1
,
Kc
Kc Kc

A5

where K P is the total thermal conductance:

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063907-10

KP =

Rev. Sci. Instrum. 79, 063907 2008

Basso et al.

K cK l
.
Kc + Kl

A6

By substitution of Eq. A5 in Eq. A1, we get

v = PTs Tb + R Pi,

A7

where
P =

KP
,
Kc

and

A8

RP = R + 1

K P
,
Kc Kc

A9

are the effective Seebeck coefficient and the effective resistance, respectively.
By substitution of Eq. A5 in Eq. A2, we get
1
qs = Pi + Ri2 K PTs Tb,
2

A10

where we defined the effective Peltier coefficient P:

P =

KP
.
Kc

A11

The thermal quantities as a function of the electric quantities

are
1
v R Pi,
P

A12

1
1
qs = Pi + Ri2 v R Pi,
2
SP

A13

Ts Tb =

where S P = P / K P = / Kc is the sensitivity.

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