Applied Thermal Engineering 117 (2017) 409–416

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Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Research Paper

Omitting the need of external heat capacity data in an adiabatic

magnetothermal setup devoted to the characterization of
nanomaterials for magnetic hyperthermia
Eva Natividad ⇑, Irene Andreu 1
Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC – Universidad de Zaragoza, Campus Río Ebro, María de Luna, 3, Zaragoza 50018, Spain

h i g h l i g h t s

Presence and arrangement of magnetic nanoparticles affect heat capacity of a medium.

We prove that heat capacity can be determined using an adiabatic magnetothermal setup.

This allows obtaining released heat power without additional heat capacity data.

Omitting external heat capacity determination saves measuring time and resources.

Accuracy increases using the same setup, specimen, conditions and temperature sweep.

a r t i c l e i n f o a b s t r a c t

Article history: The heat power dissipated by magnetic nanoparticles under alternating magnetic fields is a key param-
Received 24 November 2016 eter in biomedical applications like magnetic hyperthermia. The pulse-heating method determines the
Accepted 6 February 2017 temperature increments undergone in adiabatic conditions by a specimen due to magnetic hyperthermia.
Available online 9 February 2017
The heat power can be accurately calculated from these increments provided that the heat capacity of the
specimen is previously known. In this work, we highlight how this heat capacity, assumed to be the sum
Keywords: of the contributions of each specimen component, can present deviations due to several effects. Such
Pulse-heating method
deviations make necessary a systematic heat capacity determination for every specimen, which in turn
Magnetic hyperthermia
Heat capacity
requires adequate equipment and additional time. As an alternative, we present a new method that
Adiabatic not only provides heat capacity data but also can be implemented in the same setup used for quantifying
Radiative heat exchange the temperature increments by the pulse-heating method in adiabatic conditions. Since this method
determines the heat capacity during the time intervals between alternating magnetic field pulses, it
allows to save characterization time and resources. Eventually, it provides higher accuracy: the heating
power is obtained using just one specimen, one setup and one temperature-sweep measurement, avoid-
ing error arising from the specimen composition or measuring conditions.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction mass of MNP is mostly referred to as specific absorption rate (SAR),

Like bulk magnetic materials, magnetic nanoparticles (MNPs)
are able to convert into heat the electromagnetic energy supplied
by an alternating magnetic field (AMF). But, unlike bulk materials,
their small size turns them into highly localized heat sources, suit-
able for biological applications such as magnetic hyperthermia [1]
or heat-induced drug release [2]. The transduced power, P, per unit
⇑ Corresponding author.
E-mail address: evanat@unizar.es (E. Natividad).
1
Present address: Simon Fraser University, Department of Chemistry, 8888
University Drive, Burnaby, BC V5A 1S6, Canada.
but also as specific loss power (SLP). While the former focuses on
the fact that the transduced power is absorbed from the AMF,
the second highlights that this power is released as heat.
MNPs invest the electromagnetic energy in reversing their mag-
netic moments. The origin of the released heat it is the non-linear
and delayed response of the MNPs magnetisation with respect to
the AMF. Accordingly, SAR can be determined by either magnetic
or calorimetric methods. In the most used magnetic method, the
area of the magnetisation vs. field hysteresis loop of MNPs under
AMF is quantified (dynamic hysteresis loop). The derived energy
per cycle is adequately transformed to SAR using the AMF fre-
quency. The main limitation of this method is the unavailability

http://dx.doi.org/10.1016/j.applthermaleng.2017.02.028
1359-4311/Ó 2017 Elsevier Ltd. All rights reserved.
410 E. Natividad, I. Andreu / Applied Thermal Engineering 117 (2017) 409–416
of commercial setups working with AMF frequencies around
100 kHz and amplitudes up to 10 kA/m (tentative range for biolog-
ical applications). This is due to technical problems related to the
required fast acquisition of magnetisation data. Only a few groups
worldwide have developed special-purpose devices to overcome
these limitations [3–8].
However, calorimetric methods are the most used by far
([9–13] and references therein). Two main methods can be found
in the literature: the initial-slope method in isoperibol conditions
and the pulse-heating method in adiabatic conditions, based on
traditional adiabatic calorimetry [13,14]. In both methods, SAR is
quantified from the temporal evolution of the temperature, T(t),
of the MNPs under the AMF. Also, both require determining sepa-
rately the heat capacity (C) of the measured specimen. The former
has been found to generate unquantified errors in SAR determina-
tion due to the mismatch between the experimental conditions
and the thermal model used for relating T, P, and C [13,15,16].
The main drawback of the latter is the unavailability of a setup cap-
able of measuring T(t) in adiabatic conditions and under an AMF.
To the authors’ knowledge, there is just one apparatus (adiabatic
magnetothermal setup) operating under this method, which has
been shown to provide the most accurate P data [13,17].
Most scientific research merely evaluates SAR at room temper-
ature [9–11], neglecting any SAR variation with temperature. How-
ever, biological applications involve temperatures from 36 up to
about 50 °C. Among the abovementioned methods, only the
pulse-heating method in adiabatic conditions [18] and some meth-
ods measuring dynamic hysteresis loops [4,19] have proved to be
capable of providing SAR data as a function of temperature, SAR
(T). The former has the advantage of covering a much wider tem-
perature range. Indeed, it has allowed to show that the determina-
tion of SAR(T) at wide (even sub-ambient [18]) temperature ranges
provides valuable information about the magnetic state and prop-
erties of the MNPs [20–24]. Most importantly, this information,
similar to those provided by the out-of-phase component of the
magnetic susceptibility, is obtained with AMFs suitable for mag-
netic hyperthermia applications.
In ideal adiabatic conditions, it can be assumed that all the heat
power generated by the MNPs is invested in the specimen temper-
ature rise, and therefore the thermal power balance between the
specimen and its environment reads
dTðtÞ
P¼C
dt
As specimen, we consider a sample with a certain mass of mag-
netic nanoparticles, mMNP, dispersed in a medium, together with its
container. Integration of Eq. (1) leads to the expression for SAR cal-
culation in adiabatic conditions,
P C DT
SAR ¼ ¼ 
mMNP mMNP Dt
where DT is the specimen temperature increment during an AMF
application interval Dt, and C is assumed constant in the considered
DT. The pulse-heating method alternates P – 0 and P = 0 periods
(i.e., field-on and field-off periods) to obtain DT values at several
temperatures and assigns them to the midpoint of the temperature
interval, which is typically of a few degrees. Using Eq. (2) and the
obtained DT values, the SAR in function of temperature, SAR(T),
can be calculated, provided that C(T) is also known [18]. C is
obtained as Rcp,i  mi, where cp,i and mi are, respectively, the specific
heat capacity and the mass of each component of the specimen. For
this purpose, all cp,i(T) must be known, either from literature data or
from specific measurements, using e.g. Differential Scanning
Calorimetry (DSC). In the latter case, this involves additional
resources and characterization time.
Also, further considerations suggest that the Rcp,i  mi approach
may generate some errors due to a number of reasons. For exam-
ple, MNPs can induce significant changes in the heat capacity of
the medium they are dispersed in [22,25,26]. Also, the experimen-
tal determination of C of the SAR specimen itself is in many
instances not possible, for example using DSC, due to differences
in the specimen size and geometry required by both methods.
Moreover, the DSC characterization of volatile liquids, often used
as dispersive medium, is difficult due to sample evaporation. Also,
the scan rate used to determine cp,i(T) can modify the temperature
at which certain processes occurs, or even hinder them [27,28].
While a standard heating rate for DSC is 10 °C/min, in adiabatic
magnetothermia this rate is in general about 100 times lower,
and depends strongly on the heating ability of the specimen. To
minimize all these sources of experimental errors, it is highly
desirable to measure C and P on the same conditions and
specimens.
For this purpose, in this work we take a further step in the
determination of SAR(T) by the pulse-heating method in adiabatic
conditions. Analysing and modifying the heat transfer processes
occurring in the magnetothermal setup described in [17,18], we
have developed the first method to calculate, not only (DT/Dt),
but the whole product C  (DT/Dt) in Eq. (2) in adiabatic conditions
and using just one specimen, one temperature-sweep measure-
ment and one setup. Our method thus suppresses the need of
external heat capacity data, allowing obtaining more accurate
SAR data, while saving time and resources. In this paper, we first
evaluate the changes that the measuring parameters and/or the
presence of magnetic nanoparticles can induce in the heat capacity
of different samples. We then describe our method and its imple-
mentation in an adiabatic magnetothermal setup. Finally, the
developed method is assessed on six specimens with different C
(T) characteristics.
2. Materials and methods
2.1. Sample and specimen preparation
Three dispersive media (water, n-dodecane, n-tetracosane)
were used to produce six different samples (see Table 1): three
without magnetic nanoparticles (W, C12 and C24) and three with
magnetic nanoparticles (W-FF, C12-FF and C24-FF). Water was
ð1Þ
used as representative of biologically compatible medium, n-
dodecane as an example of the organic media used in many MNP
synthesis processes, and n-tetracosane was used as a medium
which is solid in the whole temperature range, like biological tis-
sue. These media are pure solvents whose heat capacity and melt-
ing temperature (see Table 1) are well-known, [29–33] while
different enough as to prove that the developed method can be
ð2Þ used with other media of diverse cp(T), such as physiological saline,
blood and bone.
MNPs in samples W-FF, C12-FF and C24-FF come from different
sources. The sample in W-FF is the fluidMAG-UC/C aqueous disper-
sion of Chemicell GmbH. MNPs in C12-FF and C24-FF have been
synthesized in our laboratory adapting the seeded growth method
of Sun et al. [34,35] and Luigjes et al. [36]. For this purpose, initial
6-nm spherical seeds were obtained by thermal decomposition of
iron acetylacetonate in benzyl ether in the presence of oleic acid,
oleylamine, and 1,2-hexadecanediol. Starting from these seeds,
MNPs in samples C12-FF and C24-FF were obtained using identical
seeded growth steps (2 and 26, respectively) under similar condi-
tions, but with reduced amounts of oleic acid and oleylamine,
which act as surfactants. The detailed procedures are described
in [23,24], respectively. Information about the size and shape of
all MNPs is provided in the supplementary information.
 E. Natividad, I. Andreu / Applied Thermal Engineering 117 (2017) 409–416
Table 1
Description of the samples (dispersive medium and MNP concentration) and mass composition of the measured specimens (see Section 2).
Dispersive medium Tmelting (K) Sample/specimen
Water 273 W 0.34352
W-FF
n-Dodecane 263 C12
C12-FF
n-Tetracosane 324 C24
C24-FF
Six different specimens for SAR measurement were obtained
from those six samples (and named after them). To prepare these
specimens, a portion of every sample (0.1 mL of dispersive med-
ium + MNPs if any) was enclosed inside similar silica glass contain-
ers and sealed with Nural 27 (N27, Pattex), a two-component
epoxy adhesive (see Table 1 and Fig. S1 in the supplementary infor-
mation). Table 1 collects, for each specimen, the mass of the silica
glass container (mglass), mass of the adhesive (mad), mass of the dis-
persive medium (mmed) and mass of magnetite MNPs in the sample
(mMNP).
2.2. Sample and specimen characterization
The iron content of samples C12-FF and C24-FF was determined
by Inductively Coupled Plasma – Optical Emission Spectrometry
(ICP-OES), using a Jobin Yvon 2000 setup. Samples were previously
digested in aqua regia overnight. The concentration of MNPs in
each sample was then calculated assuming stoichiometric compo-
sition of the Fe3O4 nanoparticles. This concentration (c) is collected
in Table 1 in mg of MNPs per g of sample (MNPs + dispersive med-
ium). The detailed characterization used to elucidate the MNP crys-
talline phase of samples C12-FF and C24-FF is the same followed in
[23,24], respectively (see supplementary information). MNP crys-
talline phase and concentration of sample W-FF is provided by
the supplier. Even if magnetite was found to be the main crys-
talline phase in the three samples, the presence of traces of maghe-
mite cannot be discarded. However, this presence does not alter
the work results, given the negligible contribution of the MNPs
to the additive C of each specimen, and also to the similarity of
the specific heat capacities of magnetite and maghemite.
The specific heat capacity data of samples and some compo-
nents of the specimens were either obtained from the literature
or measured by DSC, using a Q1000 device from TA Instruments
and indium and sapphire as calibrants.
The SAR data of the specimens were measured using a special-
purpose magnetothermal setup based on the pulse-heating
method in adiabatic conditions [17,18].
3. Results and discussion
3.1. Deviations among heat capacity data
As explained in the introduction, the calorimetric determina-
tion of SAR(T) values requires external C(T) data. This data is usu-
ally obtained as Rcp,imi, where cp,i and mi are, respectively, the
specific heat capacity and the mass of each component of the spec-
imen. In this section, we compare cp (T) data of some samples and
some components of the specimens in Table 1 with the aim of eval-
uating the convenience of using this additive approach. Note that
all ferrofluid samples have a MNP mass concentration lower than
25 mg per gram of sample and, therefore, the additive contribution
of the MNPs to the heat capacity is negligible.
Fig. 1(a) displays the cp values corresponding to the sample con-
tainer and the sealant used in the specimens measured in this work
411
mglass (g) mad (g) mmed (g) mMNP (g) c (mg/g)
0.01511 0.09268 ... ...
0.30376 0.02549 0.09432 2.36  103 24.4
0.37078 0.01080 0.08447 ... ...
0.31907 0.02532 0.07546 8.3  104 10.9
0.38361 0.02251 0.09495 ... ...
0.35431 0.03868 0.09587 3.9  104 4.1
by DSC. It is observed that the cp of the silica glass bought from two
different suppliers (silica glass (1) and silica glass (2)) deviates by
about 25%. Also, that the cp of the N27 adhesive slightly varies upon
aging (fresh vs. after 14 days), and that two fresh preparations (N27
(1) and N27(2)) of this two-component adhesive yield a cp differ-
ence of about 13%. This is most probably due to variations in the
adhesive component proportions leading to different curing speeds
and making the adhesives be in different polymerization stages at
the moment of DSC measurement. These results highlight the con-
venience of a systematic characterization of both components in
order to reduce errors in SAR(T) coming from C(T) deviations.
Fig. 1(b) is related with samples W, W-FF, C24 and C24-FF. On
one hand, it compares the cp of pure n-tetracosane determined in
an aneroid calorimeter [29] and the cp of sample C24-FF (n-
tetracosane + MNPs), measured in this work with DSC. The vertical
golden line indicates the melting temperature of n-tetracosane
according to [29]. The cp data of magnetite is also provided [30],
although the MNP concentration of sample C24-FF is so low
(4.1 mg/g) that the additive contribution of MNPs to C(T) is
negligible. Although at low temperature the data series of
n-tetracosane and C24-FF deviate slightly, this deviation increases
with temperature, reaching 27% at 300 K. The origin of this
deviation (setup, measuring conditions, presence of MNPs,. . .)
[22,25–28] is beyond the scope of this work, but it is evident that
the cp of C24-FF cannot be obtained as a weighted sum of those of
pure n-tetracosane and Fe3O4. On the other hand, this figure com-
pares the cp of the frozen sample W-FF (water + MNPs) measured
in this work with that of water [31,32]. It is observed that sample
W-FF undergoes premelting at about 250 K, likely due to the pres-
ence of the MNPs, and thus its cp deviates from that of ice from this
temperature on.
Fig. 1(c) shows three measurements of the cp of pure n-
dodecane (sample C12). The measurement in reference [33] was
performed in adiabatic conditions, while the other two were
obtained for the current work using DSC, either in a standard alu-
minium hermetic pan (without o-ring) or in a hermetic stainless
steel high volume pan (with o-ring). Comparing the results of the
first (blue2 continuous line) and second (black dashed line) series,
we observe that the DSC provides lower cp values when the n-
dodecane is solid (up to 12%) and just after the melting (17%). Above
the melting, the cp obtained with DSC and the standard aluminium
hermetic pan displays an upward trend, presumably due to the
vaporization heat of the n-dodecane that was able to escape the
pan, given that leakage of n-dodecane could not be avoided with this
kind of pan. The hermetic pan with o-ring was able to prevent the
leakage of n-dodecane, although the obtained data displays a wider
temperature range for the melting of C12. Even after scaling the cp
data obtained with this pan (red continuous line) to the literature
values in solid state, the cp values of the liquid n-dodecane appear
lower than those reported in [33].
2
For interpretation of color in Fig. 1, the reader is referred to the web version of
this article.
412 E. Natividad, I. Andreu / Applied Thermal Engineering 117 (2017) 409–416
Fig. 1. Specific heat capacity data of some samples and some components of the specimens in Table 1 (see Section 3.1 for further details).
Fig. 1(d) compares the cp series of pure n-dodecane according to
[33], with two successive series of that of sample C12-FF (n-
dodecane + MNPs), measured in this work with DSC. The first
C12-FF series (black dashed line) was obtained after the sample
was quenched in liquid nitrogen in presence of a static magnetic
field, so that a texture is presumably acquired and preserved by
the MNP in the frozen medium. Such texture must be lost after-
wards, upon melting of n-dodecane, given that these MNPs are
already superparamagnetic at that temperature (supplementary
Fig. S3). The second C12-FF series (red continuous line) was
recorded subsequently, after the sample was cooled inside the
DSC, i.e., the sample is non-quenched and has no texture. It is first
observed that the slope of the DSC series is different to that in [33],
due to the presence of MNPs. In addition, before the melting of n-
dodecane, the cp values of the textured C12-FF sample are up to
38% lower than those of the non-textured C12-FF, due to the differ-
ent arrangements of the MNPs. After the melting of n-dodecane,
both C12-FF series are very similar, as expected due to the lack
of texture, and display lower cp values (up to 8%) that those in
[33]. This figure then shows how, not only the presence, but also
the arrangement of the MNPs can affect the cp values in such a
way that the expression Rcp,imi does not apply.
3.2. Method for accounting for heat capacity variations in SAR data
Based on the above, it seems clear that the most adequate
determination of SAR(T) involves measuring C(T) and DT/Dt in
Eq. (2) on the same conditions, i.e., on the same specimen (same
sample portion, container and sealant), at the same temperature
sweep rate and subjected to the same magnetic field.
In order to make this possible, we have developed a method to
calculate P(T) using just one specimen, one temperature-sweep
measurement and one setup. This method was implemented in
the adiabatic magnetothermal setup described in [17,18] and
schematized in Fig. 2. In this setup, the specimen is first set under
vacuum and cooled down using liquid nitrogen. Afterwards, the
adiabatic control is enabled: the specimen environment (adiabatic
shield) is controlled to keep a certain small temperature difference
with the specimen, dT, to minimize radiation heat transfer. Finally,
the alternating magnetic field pulse sequence is launched. The adi-
abatic shield consists in a ceramic piece provided with a thin film
resistor to minimize uncontrolled self-heating in presence of the
AMF due to Foucault currents. As observed in Fig. 3, the net upward
temperature sweep is achieved by the specimen self-heating under
the successive AMF pulses, since the sample cannot be heated by
traditional means (e.g. a resistive heater) [17].
First, we have analysed the heat transfer processes occurring in
the setup. If we focus on Fig. 3(a) and (c), for dT = 0 (specimen
and adiabatic shield at the same temperature), we observe
that the specimen temperature has a downward linear trend
(0.1 °C/min) when the AMF is switched off. The origin of this
trend is that, in non-ideal but real adiabatic systems, very weak
thermal losses occur to an outer environment.
In these conditions and in absence of AMF the observed
downward slope, dT(t)/dt, is described as,
dTðtÞ
C  ¼ L½TðtÞ  T out  ð3Þ
dt
where L(W/K) is a coefficient accounting for losses and Tout stands
for the temperature of the outer environment.
Such weak downward trends have been considered and allowed
in traditional experimental adiabatic determination of heat [14],
provided that losses are small enough as to provide a linear T(t)
trend in absence of AMF and keep acceptable adiabatic conditions.
In these non-ideal conditions, it is still possible to use Eq. (2) to cal-
culate SAR through the pulse-heating method. Each DT value must
 E. Natividad, I. Andreu / Applied Thermal Engineering 117 (2017) 409–416
Fig. 2. Partial scheme of: (a) the adiabatic magnetothermal setup in [18]; (b) the modification made to the same setup (see end of Section 3.2).
Fig. 3. T(t) curves of sample C12-FF obtained using the pulse-heating method in
adiabatic conditions for (a) dT = 0 K and (b) dT = 1 K. (c) Whole measurement of the
same sample under both conditions. Inset in (c): calculated DT/Dt values under
both conditions.
be determined extrapolating the backward and forward tempera-
ture trends of every pulse, and calculating the difference of these
extrapolations at the midpoint of the heating interval Dt, as shown
in Fig. 3(a).
The downward linear trend in absence of AMF is undoubtedly a
drawback to achieve an efficient net upward trend in SAR(T) mea-
surements and therefore be able to sweep the whole temperature
range for SAR(T). Nevertheless, this situation can be reversed. Tak-
ing advantage of radiative heat transfer, the adiabatic shield can be
used as specimen heater. If it keeps a small positive temperature
difference with the specimen, dT > 0, an upward trend can be
established even in absence of AMF. In the setup described in
[17,18] and with typical specimens (supplementary Fig. S1) it
was found that acceptable adiabaticity was still maintained with
dT  1.2 K. Accordingly, Eq. (2) can be used to calculate SAR using
the pulse-heating method, as shown in Fig. 3(b) for dT = 1 K (tem-
perature of the adiabatic shield 1 K higher than that of the speci-
men). Fig. 3(c) evidences that the measurement at dT = 1 K is
much less time-consuming, taking just half the time than that at
dT = 0 K, while giving exactly the same DT/Dt values (inset of
413
Fig. 3(c)). But the advantages of these sweep conditions go much
further, since they are the starting point to the direct quantification
of P and thus of SAR, as explained in the following.
When dT > 0 the power balance can be expressed as,
dTðtÞ
C ¼ P þ R  dT  L½TðtÞ  T out  ð4Þ
dt
where the term RdT represents the heat power provided by the
radiation shield, valid for dT  T, and R(W/K) is the coefficient
accounting for the radiative power from the adiabatic shield to
the specimen (conductive and convective heat transfer between
adiabatic shield and sample is negligible in the used setup). In Eq.
(4) there are several unknown quantities: P, C and the whole last
term, which is a function that may vary with temperature in an irre-
producible manner. When the AMF is switched off, P = 0, and only C
and the last term remain unknown. In these conditions, if this last
term were negligible with respect to RdT, the heat capacity of the
specimen could be expressed as,
R  dT
C¼ ð5Þ
adT
where adT is the slope of the T(t) trend (dT/dt) when the AMF is
switched off and the temperature of the radiation shield is dT
degrees higher than that of the sample. According to this, P(T) could
be calculated from,
RðTÞ  dT DTðTÞ
PðTÞ ¼  ð6Þ
adT ðTÞ Dt
avoiding a previous determination of C(T). For this, the weak heat
power provided by the radiation shield (RdT) must be calculated.
dT is controlled and measured (and therefore known) during the
whole temperature-sweep measurement. Besides, if the parameter
R is a radiative coefficient, it must follow the law,
R ¼ r  G  T3 ð7Þ
8
where r is the Stefan-Boltzmann constant (= 5.670  10 W/
m2 K4), and G is a factor including emissivity and geometrical prop-
erties of both the specimen and the adiabatic shield. Calculation of
G then allows quantifying the heat power provided by the radiation
shield.
Fig. 3(a) and (b) highlight how the last term in Eq. (4) is, unfor-
tunately, of the same order of magnitude than (and thus not neg-
ligible with respect to) RdT in the measurements performed with
the setup schematized in Fig. 2. For example, at about 20 °C, the
slope in Fig. 3(a) (dT = 0 K), is 0.101 K/min, while that of Fig. 3
(b) (dT = 1 K) is 0.084 K/min, that is, the term accounting for uncon-
trolled losses represents 54.6% of the heat gain provided by the adi-
abatic shield when dT = 1 K.
In order to reduce the contribution of these losses, a new cera-
mic shield (outer shield) was placed surrounding the adiabatic
shield, providing a controlled-temperature outer environment for
the sample (see Fig. 2). The effect of this outer environment, whose
414 E. Natividad, I. Andreu / Applied Thermal Engineering 117 (2017) 409–416
Fig. 4. Slope of the field-off temperature trend of sample C12-FF without outer
shield (nOS) and dT = 1 K (squares) or dT = 0 K (triangles), and with outer shield
control (OS) and dT = 1 K (circles) or dT = 0 K (diamonds).
temperature follows that of the specimen, is evident (see Fig. 4):
now, the slope at about 20 °C with dT = 0 K is 0.012 K/min, while
that at dT = 1 K is 0.186 K/min, that is, the term accounting for
uncontrolled losses represents only 6.1% of the heat gain provided
by the adiabatic shield when dT = 1 K, so it can be neglected. P(T)
can now be calculated using Eqs. (6) and (7).
3.3. Assessment of the method
In order to assess the method outlined above, the value and
reproducibility of G was evaluated on the six specimens described
in Table 1. It was calculated for each sample by fitting the obtained
experimental data to the expression,
C  adT ¼ r  G  dT  T 3
where C in this equation was obtained as Rcp,i  mi.
Fig. 5(a) shows C  adT vs. T plots of the studied specimens with-
out MNPs. Specific heat capacity values for Rcp,imi calculations
Fig. 5. C  adT against T data (with dT = 1 K) fitted according to Eq. (8). (a) Specimens
without MNPs. Inset: C12 with (OS) and without (nOS) outer shield control. (b) and
(c) Specimens with MNPs (see Section 3.3).
were either obtained from the literature (n-tetracosane [29], water
[31,32], n-dodecane [33]) or measured by DSC (silica glass, adhe-
sive). Good fits to Eq. (8) were achieved in the three cases indicat-
ing, first, that our model for radiative heat exchange is valid, and
second, that for the samples without MNPs there is a good accor-
dance between the heat capacity calculated as Rcp,i  mi and that
obtained directly from adT values using Eq. (5). However, while
the obtained G values for specimens W and C12 are very similar,
that of C24 differs in 3%. This could be assigned to three main rea-
sons. First, the glass of the container is transparent to certain infra-
red wavelengths. This implies that the radiation coming from the
sample inside the container can be transmitted across it, this
resulting in slightly different emissivity values. Second, subtle vari-
ations in the specimen-shield relative position can influence the
value of G, since it depends on geometrical factors. And third, the
small thermal losses still present in the system (last term in Eq.
(4)) can also affect the G value. Note, however, that the product
C  adT against T for specimen C12 without the outer shield control
(inset in Fig. 5(a)) does not follow a T3 law, since it includes larger
uncontrolled losses. This highlights the fact that, without the use of
the outer shield control, C cannot be obtained by the simple Eq. (5)
and a unique constant G. According to the above, we considered
that assuming a mean G value ((9.2 ± 0.2)  104 m2 in our setup)
for calculations is the best option to minimize errors. Per cent
errors in Table 2 are calculated with respect to this mean value.
Fig. 5(b) displays C  adT vs. T plots of the studied specimens with
MNPs, obtained as Rcp,imi using the same contributions than those
in Fig. 5(a), and in addition that of magnetite [29–33]. Note, how-
ever, that the term accounting for the heat capacity of MNPs is neg-
ligible, due to the low mass concentrations. Similarly to specimens
without MNPs, W-FF shows good fits to Eq. (8), although with a
ð8Þ lower G value (Table 2). C12-FF and C24-FF display, however, devi-
ations from the T3 law at high T, pointing to a non-negligible influ-
ence of the MNPs in the heat capacity of the samples, not
accounted by simple addition of the contributions of the compo-
nents of the sample.
Fig. 5(c) displays C  adT vs. T plots of the studied specimens with
MNPs, obtained as Rcp,i  mi using the same contributions than
those in Fig. 5(a), except for the contributions of samples C12-FF
(n-dodecane + MNPs) and C24-FF (n-tetracosane + MNPs), for
which the DSC cp values displayed in Fig. 1 (b: C24-FF) and (d:
C12-FF, non-quenched) were used. It is observed that now the
three fits are very similar, and that deviations from the T3 law at
high T have been partially and totally corrected for samples C12-
FF and C24-FF, respectively. These results prove that the developed
method accounts for the deviations between heat capacity data
observed in DSC measurements.
In particular, DSC revealed that the cp of sample C24-FF is up to
27% lower than that of pure n-tetracosane when approaching its
melting point. Therefore, the C  adT product is overestimated when
the cp of pure n-tetracosane [29] is used to calculate C of sample
C24-FF, as seen in Fig. 5(b). The same happens to sample C12-FF
just after the melting of n-dodecane.
Table 2
Results of G calculation and per cent error (Er) of each G value (see Section 3.3).
Specimen Figure G (m2) Er (%)
W 5(a) 9.297  104 1.2
W-FF 5(b, c) 8.883  104 3.3
C12 5(a) 9.260104 0.8
C12-FF 5(b) 9.201  104 0.2
5(c) 8.943  104 3.7
C24 5(a) 8.998  104 2.0
C24-FF 5(b) 9.166  104 0.2
5(c) 8.847  104 2.6
 E. Natividad, I. Andreu / Applied Thermal Engineering 117 (2017) 409–416
Fig. 6. SAR(T) data for sample C12-FF, measured with AMF amplitude and
frequency of 3.3 kA/m and 108 kHz, respectively (see text). Data at the melting
temperature interval is omitted.
The deviations from the T3 law at high T still observed in Fig. 5
(c) for C12-FF could have an origin in the measuring conditions
during SAR determination. On one hand, DSC measurements
showed that sample C12-FF (n-dodecane + MNPs) presents a
higher cp than that of n-dodecane in the frozen state, but may
undergo reductions of up to 38% upon MNP texturing under a static
magnetic field. Even if SAR measurements do not take place under
static fields like the ones used for texturing, AMFs can also induce
organization of MNPs [37], whose effect on the real C cannot be
easily quantified with commercial DSC equipment. Contrary to
what it is observed in Fig. 1(d), the influence of the AMF effect
should only be present at high T. In the magnetothermal setup,
the specimen C12-FF was solidified in absence of AMF, so that
organization due to the AMF can occur only during the SAR mea-
surement, and only after the melting of n-dodecane. Therefore this
effect can explain the deviations observed at high temperature. On
the other hand, the volume of the glass container of specimen C12-
FF is occupied with ferrofluid to a high percentage, see supplemen-
tary Fig. S1. It is also possible that pressure effects can affect cp
after the melting of n-dodecane.
Fig. 6 shows the SAR values of sample C12-FF obtained using
‘‘calculated” heat capacity (last term in Eq. (2) and Rcp,i  mi) and
‘‘directly measured” adT values (middle term in Eqs. (2) and (6))
without any additional cp data. The ‘‘calculated (1)” series was
obtained using cp values obtained from the literature (n-
dodecane [33], magnetite [30]) and measured by DSC (silica glass,
adhesive). The ‘‘calculated (2)” series was obtained using cp values
measured by DSC (sample C12-FF, silica glass, adhesive). Even if
data at the melting temperature interval of n-dodecane are omit-
ted, due to the impossibility of obtaining correct adT values at this
interval (T is nearly constant during the melting), data down to
10 K below the melting temperature differ appreciably between
calculated and directly measured values. This is most probably
due to the particular measuring conditions in the adiabatic magne-
tothermal setup (e.g., very low temperature sweep rate), which
slightly affect the melting process of n-dodecane. Therefore, the
SAR values obtained using the measured adT values not only
account for the above mentioned variations in C, but also provide,
in this case, a better defined SAR maximum, located just at the
melting interval of n-dodecane. In sum, the technique here pre-
sented outperforms the traditional way of quantifying SAR through
the combination of cp values (DSC, literature) and temperature
increments during AMF application (adiabatic magnetothermal
setup).
4. Conclusion
This work has pointed out that the determination of the heat
capacity can be a source of error in the calculation of the heat
power dissipated by nanomaterials for magnetic hyperthermia,
415
since this magnitude can be affected appreciably by the presence
and arrangement of magnetic nanoparticles, or when using differ-
ent measuring conditions.
As an alternative to the systematic determination of heat capac-
ity for each specimen, a method is proposed that allows the direct
calculation of the heat power without the need of additional heat
capacity data. This method not only suppresses the necessity of
knowing previously the mass and specific heat capacity of each
specimen component, but also allows the determination of all
the required data for heat power calculation with the same setup,
on the same specimen, under the same measuring conditions and
during the same temperature-sweep run. This, in turn, avoids dis-
crepancies arising from the use of different specimens or measur-
ing conditions to determine temperature increments and heat
capacity, and thus increases accuracy in SAR(T) data.
Acknowledgements
This work has been funded by the Spanish MINECO and
FEDER under project MAT2014-53961-R. I. Andreu thanks the
Spanish CSIC for her JAE-Predoc contract. The authors thank
O. Roubeau for the DSC measurements. The use of Servicio General
de Apoyo a la Investigación-SAI, Universidad de Zaragoza is also
acknowledged.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.applthermaleng.
2017.02.028.
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