Journal of the Korean Ceramic Society Review

http://dx.doi.org/10.4191/kcers.2011.48.6.577
Vol. 48, No. 6, pp. 577~583, 2011.

Electron Spin Resonance (ESR) and Microwave Absorption Studies of

Superparamagnetic Iron Oxide Nanoparticles (SPIONs) for
Hyperthermia Applications

Yongho Choi, Terry Yi, Joo Seok Park, and Do Kyung Kim,
Department of Materials Science and Engineering, Jungwon University, Goesan 367-805, Korea
Department of Sports Medicine, Jungwon University, Goesan 367-805, Korea
Department of Biomedical Science, Jungwon University, Goesan 367-805, Korea
Korea Institute of Ceramic Engineering and Technology, Seoul 153-801, Korea
(Received September 26, 2011; Revised October 23, 2011; Accepted October 25, 2011)

ABSTRACT
Stabilized biocompatible superparamagnetic iron oxide nanoparticles (SPIONs) were prepared by controlled coprecipitation
method for hyperthermia application. ESR measurements determined that all of the interactions in the individual SPIONs (1 nm
and 11 nm) were antiferromagnetic in nature because the ions contributed to the magnetization with a range of magnetic
moments. In-situ monitoring of the temperature increment was performed, showing that the microwave absorption rate of the
SPIONs was dispersed in an appropriate host media (polar or non-polar solvents) during microwave irradiation. Microwave
absorption energy rates and heat loss of SPIONs in solvent were calculated by non-linear data fitting with an energy balance
equation. The microwave absorption rates of SPIONs dispersed in solvent linearly increases when the concentration of SPIONs
increases, implying that the microwave absorption rate can be tunable by changing the concentration of SPIONs.
Key words : Magnetite, Superparamagnetic, Iron oxide, Nanoparticles, Microwave absorption, ESR, SPIONs

1. Introduction In thermal ablation, a tumor is subjected to high temperatures

C
(> 46oC, up to 56oC) causing cells to undergo direct tissue
urrent available treatments for cancer patients include necrosis, coagulation or carbonization. Moderate hyperthermia
hyperthermia,1) chemotherapy,2) radiation therapy,3) sur- (41oC < T < 46oC) has various effects at both the cellular and
gery, gene therapy,4) and immunotherapy.5) Hyperthermia is tissue levels. Diathermia uses lower temperatures (T < 41oC)
the generation of heat; with respect to cancer therapy, to treat rheumatic diseases in physiotherapy. During moderate
hyperthermia is treatment wherein heat is generated at the hyperthermia, which is traditionally termed as hyperthermia
tumor site, changing the physiology of diseased cells and finally treatment, cells undergo heat stress in the temperature range
leading to apoptosis. Methods for heating the whole body include of 41-46oC, resulting in activation and/or initiation of many
using hot wax, hot air, hot water suits, infrared, radiofrequency intra- and extracellular degradation mechanisms, such as
(RF), microwave, ultrasound, hot blood, and blood perfusion. protein denaturation, protein folding, aggregation, and DNA
Experimental and clinical reports indicate that local heating cross-linking. With a single heat treatment, permanent irre-
has promising potential for hyperthermia therapy, but it is versible protein damage can occur, resulting in protein
difficult to generate and regulate the temperature in tumors aggregation and/or inhibition of many cellular functions.7)
and normal tissues while minimizing the deleterious effects Several reasons have been suggested for the limited amount
of hyperthermia. One way to control the temperature is by of heat arising in tumor tissue during hyperthermia treat-
manipulating two important magnetic properties of the mag- ment. The temperature difference between the tumor and
netic nanoparticles: magnetization and coercivity. These two surrounding normal tissue are generally attributed to the
properties are related to the heating efficiency and Curie difference in blood flow in normal tissue. Another possible
temperature, so they can be adjusted slightly above the thera- reason is that tumor cells are sensitive to heat due to their
peutic temperature. Self-regulating heating mediators could hypoxic, acidic, and poor nutritional states. During hyperthermia
potentially be developed once methods for sufficient heating treatment, the heating also increases the membrane perme-
are improved.6) ability of some drugs, which has led to hyperthermia being
combined with chemotherapy.
In magnetic fluid hyperthermia (MFH),8) superparamagnetic

Corresponding author : Do Kyung Kim iron oxide nanoparticles (SPIONs) are intravenously injected
E-mail : [email protected] into the body as mediators that selectively diffuse into cancerous
Tel : +82-43-830-8606 Fax : +82-43-830-8679 tissues. When a high-frequency alternating magnetic field

577
578 Journal of the Korean Ceramic Society - Yongho Choi, Terry Yi, Joo Seok Park, and Do Kyung Kim Vol. 48, No. 6

(AMF) is added, the SPIONs heat up, raising the temperature frequency range is not optimistic for medical uses, because
of the tumor cells without adverse effects to the surrounding organs and cells include an abundance of water molecules.
healthy tissue. The generated heat can be controlled using Even though 2,450 MHz microwave is not a proper frequency
SPIONs with an adaptable Curie temperature, which is tunable for hyperthermia, this frequency can be used to interpret the
by varying the chemical compositions, particle size, and surface microwave absorption and heating mechanisms of SPIONs,
modifications of the SPIONs. because the absorption mechanisms will be similar to other
SPIONs have recently been highlighted in various nano- microwave frequency ranges. However, a non-polar solvent
medicinal areas, as MR imaging agents, drug delivery vectors, was used, since polar solvents can be stimulate by a 2,450 MHz
drug-targeting agents, and as hyperthermia mediators via microwave. For the case of polar solvent, the heating profile of
intravenous or extravenous injection. For example, in the early the solvent was recorded as a control experiment and subtracted
stages of tumors, it is difficult to diagnose and identify lesions from the heating profiles of SPIONs dispersed in solvent.
using only MR imaging, because of its low sensitivity and limited To predict the proper amount of SPIONs and the appropriate
detection. The intensity of the MRI signal must be drastically exposure time to SPIONs for in-vivo hyperthermia, this study
enhanced through the introduction of contrast agents, i.e. analyzes the heating mechanisms of SPIONs in non-polar
paramagnetic Gd-EDTA and SPIONs, which induce precession solvent under microwave irradiation. We suggest and dem-
and resonance more than water molecules. Furthermore, onstrate indirect interpretation of the microwave absorption
SPIONs techniques can also be used for in vitro gene trans- rate by monitoring the temperature increment of SPIONs
fection. In this case, a high-field, high-gradient is positioned dispersed in either polar or non-polar solvents during microwave
under the multi-well plate, culture flask, or petri dish in which irradiation. In the same manner, this approach will be useful
the cells are growing. The fundamental principle is that thera- for predicting the amount of SPIONs and the exposure time
peutic agents are attached to, or encapsulated within, micro- when microwave generators of any frequency range are used
or nanoparticles. These carrier vectors may have magnetic cores as heating devices. For example, SPIONs dispersed in oil can
with biocompatible and biodegradable polymers, which can be be can be used as a column heater, and the heating element can
further functionalized with therapeutic chemicals, or they be replaced by a magnetron. In this case, heating and energy
may consist of mesoporous polymers that contain SPIONs efficiency will be much higher than a conventional oil heater,
precipitated inside the pores. By functionalizing the polymer similar to the case of a microwave oven. To design such an
or metal coating, it is possible to attach (for example) cytotoxic appliance, the amount of SPIONs and exposure time must
drugs for targeted chemotherapy or therapeutic DNA to correct be calculated based on the suggested approach.
a genetic defect.9)
When an electromagnetic field is used as energy deposition, 2. Experimental Procedure
the influencing aspects are a complex function of frequency,
intensity, polarization of the applied fields, geometry, and size 2.1. Materials
of the SPIONs. Several variable factors need to be taken All chemicals were of reagent grade and were used without
into account to regulate the desired target temperature for further purification. Ferric chloride hexahydrate (FeCl36H2O >
hyperthermia, including electron spin resonance (ESR),10) energy 99%), ferrous chloride tetrahydrate (FeCl24H2O > 99%), sodium
deposition, thermal conductivity in the membrane, and particle hydroxide (NaOH, 99%), and concentrated hydrochloride
transports between the membranes. Extensive technical effort, (HCl, 99%, 12N) were obtained from Sigma-Aldrich. Milli-Q
advanced therapy, and thermometric systems are required water was re-deionized (specific conductance < 0.1 s/cm) and
to resolve these issues, because experimental hyperthermia deoxygenated by flowing N2 gas for 1 h prior to use.
requires thermal homogeneity in target legions with a con-
trolled temperature. 2.2. Preparation of superparamagnetic iron oxide
Whether or not the SPIONs are administrated to the tissue, nanoparticles (SPIONs)
ESR is the major phenomenon under external magnetic field, SPIONs with an average particle size of 1 nm were prepared
RF, or microwave irradiation. Microwave heating devices for without any additional stabilizer according to the following
hyperthermia are already commercially available, using fre- procedure. Typically, 5 mL of iron solution containing 1
quencies of 434 MHz, 915 MHz and 2,450 MHz. These devices 10-2 M Fe2+ and 2 10-2 M Fe3+ was added dropwise into 50 mL
use a microwave generator, including a helical antenna, which of 8 10-1 M NaOH under vigorous mechanical stirring
is moderately different from the conventional microwave oven, (2,000 min-1) for 30 min at room temperature. The color of the
used as a household appliance. The specially designated suspension changed to black almost immediately. SPIONs
microwave heating device for hyperthermia can localize the with a particle size of 11 nm were prepared by increasing the
frequency on the target area, i.e. the lesion, instead of full body reaction temperature. All of the procedures and experimental
heating. In general, an output frequency of 915 MHz with a conditions were the same as the above procedure, except 1
maximum power of 60 watts is permitted for medical use, 10-1 M Fe2+ and 2 10-1 M Fe3+ was added dropwise into 50 mL
because it requires no RF shield enclosure. It is well known that of 8 10-1 M NaOH alkaline solution. The product was heated
water molecules can be stimulated by a 2,450 MHz microwave, to 80oC for 30 min under magnetic stirring. The precipitated
which is used for household appliance. Because of this, that powders were collected and removed from the solution by
November 2011 Electron Spin Resonance (ESR) and Microwave Absorption Studies of Superparamagnetic Iron Oxide Nanoparticles (SPIONs) for.... 579

applying an external magnetic field. The supernatant solution sized SPIONs. A commercial temperature controller was used
was removed from the precipitate after decantation. Deoxy- to adjust the temperature, having an accuracy of 1 K. The
genated Milli-Q water was added to wash the powder and relative orientation of the external field and the experimental
the solution was decanted after centrifugation at 3,500 min-1. sample axes was determined with a goniometer. The magnetic
After washing the powder three times, 1 10-2 M HCl solution field component of the microwave field always remained
was added to neutralize the anionic charge on the surface of perpendicular to the DC field. Small amplitude, 100 kHz AC
the particles. The positively charged colloidal particles were magnetic field was applied parallel to the DC field in order
then separated by centrifugation and peptized by adding to record the field-derivative ESR absorption signal.
deoxygenated Milli-Q water. For ESR measurements, the
sample was dried in a vacuum oven at 120oC for 12 h. Based 3. Results and Discussion
on the XRD measurements, the size of SPIONs nanoparticles
was 1 and 11 nm. 3.1. Synthesis and characterization of magnetite
nanoparticles
2.3. Microwave absorption The chemical reaction of Fe3O4 precipitation is given by:
A commercially available microwave oven operating at a
maximum power level of 800 W was used in this study. The Fe2+ + 2 Fe3+ + 8 OH- Fe3O4 + 4 H2O (1)
oven was equipped with a K-type thermocouple attached to
a data acquisition system using a PC. The diameter of the According to the results of thermodynamic modeling of
thermocouple is important for increasing S/N inside the this system, a complete precipitation of Fe3O4 is expected in
microwave cavity. A stainless steel shield with a diameter of the pH range pH = 7.5-14, while maintaining a molar ratio
1.5 mm was used to effectively shield the thermocouple from of Fe2+ : Fe3+ = 1 : 2 under a non-oxidizing environment. Under
the microwave field. Domestic microwave ovens operate over oxidizing conditions, Fe3O4 may be oxidized, as given by the
the entire power range in alternating cycles, from maximum following equations:
to zero.11) The frequency of the maximum power cycle is rep-
resented by a power level number. For example, power level Fe3O4 + 0.25 O2 + 4.5 H2O 3Fe(OH)3 (2)
2 means that the magnetron is actually on for an average of
2 s out of every 10 s, whereas power level 10 represents con- Fe3O4 + 0.25O2 + 1.5Fe2O3 (3)
tinuous radiation.
100 mL of cyclohexane/toluene containing a certain amount Aqueous dispersion of superparamagnetic iron oxide
of magnetite was placed in a Teflon container and inserted into nanoparticles was prepared by adding an aqueous mixture
the microwave cavity. All the experiments were performed of ferric and ferrous salts to a strong alkaline solution at
at a fixed volume (100 mL) and a fixed container position in the room temperature. In the present study, a solution of NaOH
cavity. Microwave enhancements were determined by com- was used as alkali source, instead of ammonia. Oxygen is
paring the data sets obtained using similar time steps of eliminated from the solution by flowing N2 gas through the
microwave irradiation. reaction medium during synthesis operation in a closed system.
Black magnetite is precipitated when the iron source is
2.4. Characterization of SPIONs added to the NaOH in the presence of N2. Methods for aiding
A TEM study was carried out on a JEOL-2000EX microscope in the precipitation of magnetite include vigorous mechani-
with an electron kinetic energy of 200 kV. The specimen for cal mixing for 30 min, addition of approximately 50 vol% of
TEM imaging was prepared by suspending the SPIONs in acetone, and use of an external magnet at the bottom of the
deionized water by sonication for 3 min. After ultrasonic reactor. The supernatant is removed and replaced by a mixture
dispersing, 1 mL of the SPIONs suspension was centrifuged of 50 vol% deionized water and 50 vol% acetone. After decanting
for 5 min at 14,000 min-1. A drop of well-dispersed supernatant several times, the precipitate is divided into two portions. The
was placed on a carbon-coated 200 mesh copper grid, and first is dried in an oven at 120oC for 2 h and used as a powder
the sample was then dried under ambient conditions before for physical measurements. The other is redispersed in a
being attached to the sample holder on the microscope. proper aqueous solution as a ferrofluid and used for the
The Electron Spin Resonance (ESR) measurements were absorption behaviors of microwave irradiation.
performed as a function of temperature with average particle When the concentration of the NaOH solution is increased
sizes of 1 and 11 nm in diameter. The ESR spectra were recorded from 0.9 to 1.5 M at a pH = 14, the crystal size increases from
with a Bruker spectrometer operating in the X band (9.5 GHz) 13 to 30 . On the other hand, the pH of the solution also
and interfaced to a PC with Stelar software for data acquisition plays an important role in controlling the crystal size. For
and handling. The sample was mounted in a microwave cavity solutions of 1.5 M NaOH, decreasing the pH from 14 to 11.5
placed between two poles of an electromagnet, providing a has been shown to increase the particle size from 30 to 60 .
DC field up to 1.6 T. An Oxford continuous helium gas flow The particle size distribution and morphology were examined
cryostat, operating in the temperature ranges 4-300 K, was by TEM analysis. A Langmuir film was prepared on a TEM
used to study the temperature dependence of the different grid in order to prepare a monodispersed magnetite layer. A
580 Journal of the Korean Ceramic Society - Yongho Choi, Terry Yi, Joo Seok Park, and Do Kyung Kim Vol. 48, No. 6

volume of 100 L of magnetite in oleic acid was redispersed

in 100 mL toluene with a strong sonification and the agglomer-
ation was precipitated using a centrifuge. Then, 1 mL of fer-
rofluid was taken from the supernatant and redispersed in
100 mL toluene under strong sonification. The agglomeration
was precipitated using a centrifuge and stabilized for 1 h
before the 100 L of the magnetite solution was removed
from the top of the solvent and dropped into a deionized water
bath, forming a thin Langmuir film on the surface of the water.
The film was transferred onto a TEM grid using a horizontal
dipping technique. As shown in Fig. 1, the SPIONs primarily
consist of almost perfect mono particles, though their morphology
ranges from ovular to spherical. The size distribution was
calculated using an equation based on a log-normal function,12)
yielding an average particle diameter of 72 with a standard
Fig. 2. ESR intensity versus temperature of 1 and 11 nm
deviation d = 0.2. This value is close to the crystal size calculated superparamagnetic iron oxide nanoparticles (SPIONs).
from XRD data (60 ). The X-ray diffraction patterns show
very low crystallinity at the interface, which induces a change
in the magnetocrystalline anisotropy. The magnetic diameters, a function of temperature, showing a behavior similar to typical
calculated from the Langevien equation, are also smaller than spin-glass materials. Therefore, the magnetic moments of
those determined by TEM. When the magnetite nanoparticles the individual 1 nm SPIONs are disordered throughout the
are crystalline, the interactions between the particles are larger sample, resulting in a sharp decrease in the magnetization
than low crystalline particles. The magnetic size of the magnetic as averaged over all possible random directions of the magnetic
nanoparticles dispersed in a fluid and in powder form is moments in single domain particles, due to spin frustration
reported in a previous paper.13) below 50 K. In particular, 11 nm SPIONs show a very broad
maximum with respect to temperature. The magnetic anisotropy
3.2. Electron Spin Resonance (ESR) energy Ea is proportional either to the volume or to the surface
The microwave absorption by the sample is proportional of the particles in a single domain particle and becomes
to the imaginary component of the high frequency magnetic comparable with the thermal energy (kBT).
susceptibility. This susceptibility generally shows a resonance This effect is supported with the line width (Hpp) data
property with respect to the field due to Larmour precession given in Fig. 3. At low temperatures, the Hpp of 1 nm SPIONs
of the magnetic moments around the DC magnetic field. The rapidly increases and doubles with respect to that of 11 nm
resonance field values and line width are determined by mag- SPIONs. The decline of Hpp at low temperature is related
netic free energy and relaxation parameters, respectively. While to the fact that the whole system can be considered magnetically
the first integral of the field-derivative ESR signal represents solid, so relaxation times become longer, which is consistent
the AC susceptibility, the second integral is proportional to to with the observed narrowing of ESR lines at low temperature.
the DC susceptibility. Therefore, ESR spectra present valuable At low temperatures, Hpp of the ESR spectra increases,
information, including the DC and AC magnetic properties showing linear temperature dependence. However, there is
of the sample.
Fig. 2 shows the ESR spectra intensity of 1 nm SPIONs as

Fig. 1. TEM images of bare superparamagnetic iron oxide

nanoparticles (SPIONs) prepared by coprecipitation
method. The crystal sizes of (a) 1 nm and (b) 11 nm Fig. 3. ESR line-width versus temperature of 1 and 11 nm
were measured by XRD. superparamagnetic iron oxide nanoparticles (SPIONs).
November 2011 Electron Spin Resonance (ESR) and Microwave Absorption Studies of Superparamagnetic Iron Oxide Nanoparticles (SPIONs) for.... 581

a deflection from linearity at very low temperatures. This Hpp promotes either ferromagnetic or antiferromagnetic order,
could be immediately ascribed to the dipolar interactions according to the position of the surrounding particles around a
between the SPIONs. The decrease in the heterogeneity of certain magnetic particle. Because of the magnetic interaction,
the dipolar fields could be expected due to the ordering of the the system is forced into a disorder, since the spin glass behavior
SPIONs. However, it was also expected that the linear tem- cannot be attributed solely to the dipolar interactions. In
perature would be dependent on the magnetization parallel to particular, Hpp for 1 nm SPIONs is too high (3 kG) to be
the increments of magnetic moments of the individual particles, explained by dipolar interactions between the particles. If
but the experimental results shown in Fig. 2 contradict this this value is attributed to heterogeneous dipolar field distri-
prediction. That is, at low temperatures, the disorder of the butions, this dipolar field must be at least 3 kG, contrary to
dipolar fields increases because the magnetization is not the theoretical predictions. In these experiments, powders were
increasing at the same rate, which could be due to the effect diluted in paraffin in order to avoid dipole-dipole effects in the
of some antiferromagnetic interactions, thereby increasing the Hpp parameter. However, sufficient homogeneity of the
disorder of the system and enhancing the line broadening. diluted sample could not be achieved due to magnetic dipole-
Effective g-values, which can be derived from the measure- dipole interactions between the particles.
ment of the magnetic field at the center of the ESR spectra, are On the other hand, the crystal structure of the ferrites changes
given in Fig. 4. The temperature dependence of these values from cubic to orthorhombic at low temperatures and the
shows a linear behavior. The tendency of the g-value (the magnetization is slightly decreased. Moreover, the slight
spectrum is shifted to the lower fields) shows an increase in the deviation from stoichiometry makes it difficult to achieve the
internal fields. This result is consistent with the line width maximum magnetization and widens the hysteric curve.
results and both lines are superpositioned. The increment in
effective g-values at low temperature should be attributed to 3.3. Microwave absorption by SPIONs
the exchange anisotropy due to antiferromagnetic interactions To analyze the temperature profiles for these experiments,
between the SPIONs. Actually, the microscopic interactions conservation of energy was applied, considering the liquid
of individual particles are antiferromagnetic, resulting in sample to be homogeneous and isotropic. The conversion of
ferrimagnetic order. These antiferromagnetic microscopic inter- microwave energy to thermal energy is governed by the
actions increase both the line width and the effective g-values. relation15):
The main contributions to the Hpp come from these interac-
tions, as shown by Aktas14) in a study performed on a epitaxial T- = (T) +
C ------ (4)
Q
t
single crystal Fe3O4 film on MgO substrate. Fig. 4 shows results
consistent with Aktas for 11 nm SPIONs, but the effect is more where C is the heat capacity per unit volume, is the mass
apparent. Therefore, the increase in the effective microscopic density, T is the temperature (oC), t is the time(s), is the

fields at low temperatures is obvious. In spin glass systems, Boltzmann constant, and Q is the microwave energy absorp-
this microscopic local field can usually be attributed to the tion rate(J/s).
exchange anisotropy.14) Holzwarth et al.16) used a more simplified energy balance
In conclusion, both samples show superparamagnetic between the glass container and the sample in the microwave
behaviors. There are well-known dipole-dipole interactions cavity. A Teflon container was chosen to avoid hybrid-heating
between the magnetic nanoparticles. This dipolar interaction effects, as a pre-experiment with a glass container showed
that the glass was heated more than the sample. So, the
energy equation was modified for a Teflon container:

dT dT
Q = mSCps ------- + mCCpc ------- + kS( T T0) (5)
dt dt
where Q is the microwave energy absorption rate (J/s), S is
the surface area of the container exposed to microwave irra-
diation (m2), k is the heat-transfer coefficient (J/m2oC s), T is
the temperature of the sample (oC), T0 is the initial temperature
of the system (oC), m is the mass (kg), Cp is the heat capacity
(J/kgoC), t is the time (s), and the subscripts s and c denote
the liquid sample and the Teflon container, respectively.
Therefore, the solution of Eq. (5) is:

A-(1 exp ( Bt))

T = T0 + --- (6)
B
In Eq. (6), A (oC /s) and B (s-1) denote the rates of energy
Fig. 4. geff values versus temperature of 1 and 11 nm super- absorption and heat loss for the microwave-irradiated system,
paramagnetic iron oxide nanoparticles (SPIONs). respectively. Values of these parameters were obtained for
582 Journal of the Korean Ceramic Society - Yongho Choi, Terry Yi, Joo Seok Park, and Do Kyung Kim Vol. 48, No. 6

variously heated samples by non-linear fitting Eq. (6) to the fields converts the radiation energy to heat.17) The SPIONs
experimental results. coupled with the microwaves and increased the friction between
Microwave absorption experiments were performed at the particle and molecule. When the concentration of the
2.45 GHz with 800 W of irradiation output. A Teflon-shielded SPIONs is increased in the solvent, the friction between the
thermocouple was used to monitor the temperature change. particle and polar solvent also increased, resulting in the linear
Temperature fluctuations due to electromagnetic noise inside increase in the microwave absorption rates.
the sample were confirmed by a standard thermometer, after
the main power was turned off. Abnormal temperature profiles 4. Conclusions
were occasionally observed due to non-homogeneous microwave
fields in the cavity. When this happened, the power was turned For application in hyperthermia, SPIONs with a diameter
off and the experiment was repeated until the temperature of 11 nm were prepared by controlled coprecipitation. Although
profile was reproducible. Digital data was recorded every a ferrimagnetic order makes it possible to get very high
ms with a data acquisition system that allows the data to be magnetization values, the exchange interactions are anti-
best fit using Eq. 6. Data fitting was performed with a common ferromagnetic and the dipolar interactions are either ferro-
fitted value for B (so that the heat-transfer coefficient was magnetic or antiferromagnetic, so it is not surprising to get a
the same for all experiments), allowing A to take different disordered spin profile known as spin-glass. The enormous
values for each run. The microwave absorption rates for polar increase in line width of the ESR spectra can be correlated
and nonpolar solvents are significantly different, since polar to the distribution of exchange interaction. Indirect electron
molecules easily couple with microwaves and rapidly produce magnetic resonance experiments in the microwave cavity at
heat, while nonpolar molecules cannot couple with microwaves. 2.45 GHz with 800 W of irradiation output were performed.
In general, the heat generation in the microwave field is This approach allows for the prediction of heating mechanisms
caused by ionic polarization and dipole rotation of solvent as a result of the excitation of unpaired electrons of iron, effects
molecules. Consequently, the polarity index (P) of the solvent of coating agents, particle size, and volume fraction. The
is an important factor for the microwave absorption rate. efficiency for converting microwave irradiation to thermal
The microwave absorption rate, A, for water (P = 10.2) and energy is predicted by applying the conservation of energy to
cyclohexane (P = 0.2) in a Teflon container were 1.55C s-1 a differential volume. The rates of heat loss and energy
and 0.833C s-1, respectively. The microwave absorption rate absorption are obtained by non-linear fitting of the experi-
of water is approximately twice as fast as cyclohexane. Fig. 5 mental data.
presents the temperature profiles as a function of microwave
irradiation time for water and magnetite colloids in toluene Acknowledgment
(P = 2.4) containing different concentrations of magnetite
particles with a diameter of 11 nm. The unpaired electrons This research was supported by the Basic Science Research
(Fe2+, Fe3+) are excited to a high energy state by the absorption Program through the National Research Foundation of Korea
of microwaves. The excited electron then changes its spin (NRF), funded by the Ministry of Education, Science and
direction and relaxes into a ground state by emitting phonons. Technology (Grant No. 2011-0013675).
The coupling between the magnetic dipoles and microwave
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