Journal of Magnetism and Magnetic Materials 530 (2021) 167938

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Journal of Magnetism and Magnetic Materials

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The effect of the particle size on the heating and drug release potential of
the magnetic nanoparticles in a novel point of view
Majid Abdellahi, Mohammad Tajally *, Omid Mirzaee
Faculty of Materials and Metallurgical Engineering, Semnan University, Semnan 35131-19111, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: The present study is written to provide an overview of the effect of the particle size on the heating and drug
SrFe12O19 ceramic nanoparticles release potential of the magnetic materials under magnetic fields. As a symbol representing the change of particle
Superparamagnetic size, a dimensionless σ parameter is defined by dividing anisotropic energy by the thermal one. According to the
Ferromagnetic
obtained results, at the boundary of ferromagnetic and superparamagnetic nanoparticles (σ≈1), there is the
Particles size
Magnetic hyperthermia
maximum heat production. On the other hand, single-domain nanoparticles with the largest size (σ≫1) have the
lowest releasing heat under AC magnetic field. There is also a considerable heat production under AC magnetic
fields for both superparamagnetic (σ < 1) and soft-ferromagnetic materials (σ > 1). However, the results are
significantly different when MNPs are used as heating cores in drug release systems. Here, the soft-ferromagnetic
materials have a low heating and hence low drug release potential. According to the results obtained, increasing
σ causes three important events. The first is the reduction of the spin canting effect which results in the
amplification of the spin rotations in the same direction and hence a higher potential of Neel heating mechanism.
The second is the growth of the macrospin size which leads to more spin torque and hence more heating energy.
The third is blocking the macrospin and consequently activation of the Brownian heating mechanism. However,
the results are significantly different when MNPs are used as heating cores in drug release systems. Here, the soft-
ferromagnetic materials have a low heating and hence low drug release potential. As a reason one can say that in
drug release systems, there are barriers to activation of the Brownian mechanism which reduce the heating and
drug release potential of soft-ferromagnetic nanoparticles.

1. Introduction magnetic properties of nanoparticles [7]. This factor plays an essential

role in the conversion of superparamagnetic to ferromagnetic properties
One of the most important characteristics of magnetic nanoparticles in materials [8-10].
(MNPs) is transforming the electromagnetic energy into heat, under The particle size reduction can reach the point that a particle con­
magnetic fields [1,2]. This phenomenon is known as magnetic hyper­ tains only a single domain [11]. This single-domain nanoparticle, once
thermia in which the generated heat destroys cancer cells or pathogenic formed, has a large macrospin with high anisotropy energy [12]. The
microbes [3]. heat generated from the atomic vibrations is not able to rotate this
Another application of magnetic hyperthermia can be found in drug macrospin [13] and a magnetic field is required for this purpose. In this
release systems, where magnetic nanoparticles are used as cores and case, the material has a hard-ferromagnetic mode [13] with high
thermoresponsive polymers as coatings. [4-6]. In fact, above the lower amount of coercivity (Hc). As the particle size decreases further, the
critical solution temperature (LCST), the polymer undergoes reversible anisotropy energy also decreases and the coercivity tends to lower
volume loss as a result of the expulsion of hydrophobically bound water values, during which a soft-ferromagnetic material is formed [13]. In
from the polymer chains. Below of LCST the polymer absorbs water and this case, the macrospin becomes smaller than before, but it is still
re-expands. The heating potential of MNPs under AC magnetic fields can resistant to thermal energy (resulted by the atomic vibration) and does
affect the thermoresponsive polymers to release drug above their LCST not rotate. If the particle size reduction continues to a critical extent, the
[4-6]. anisotropic energy becomes very limited and macrospin is released from
Particle size is one of the most important factors in changing the the anisotropy field. Here the heat generated by the atomic vibration can

* Corresponding author.
E-mail address: m_tajally@[Link] (M. Tajally).

[Link]
Received 20 November 2020; Received in revised form 7 March 2021; Accepted 14 March 2021
Available online 23 March 2021
0304-8853/© 2021 Published by Elsevier B.V.
M. Abdellahi et al. Journal of Magnetism and Magnetic Materials 530 (2021) 167938

rotate the macrospin and a superparamagnetic mode will be formed 2 days (48 h). The lyophillizer was maintained at a temperature of −
[13]. 47 ◦ C during this process. The end product of this process resulted in a
According to the above description, it was found that the heating dry porous scaffold.
potential of nanoparticles in superparamagnetic mode is quite different X-ray diffraction (XRD) spectra using Cu-Kα radiation, in the 2θ
than that of ferromagnetic one, and particle size plays a decisive role limitation of 20-80◦ , was used to find the crystalline size and the rate of
here. the phase formation progress. The magnetic properties including satu­
There have been many reports about the use of ferromagnetic [14- ration magnetization (Ms) and also coercivity (Hc) of the samples were
16] and superparamagnetic nanoparticles in magnetic hyperthermia determined by using a vibrating sample magnetometer (VSM, Meghnatis
[3,17,18]. Some of these reports have confirmed the superiority of Daghigh Kavir Co., Iran) at room temperature. Field emission scanning
ferromagnetic materials, while the others have reported that super­ electron microscopy (FE-SEM) and transmission electron microscopy
paramagnetic materials are more suitable for magnetic hyperthermia. (TEM, Philips CM30) with an operating voltage of 200 Kv, were used to
This is a very important challenge because the use of a more optimal morphological observations. The size of nanoparticles was determined
substance, causes the reduction of its rate of the consumption and hence using particle size analysis (PSA) tool (model Nano ZS461). To investi­
its toxicity in in-vivo conditions. gate the heat generation of the samples, magnetic nanoparticles were
In the present work, the role of particle size in separating super­ placed inside a thermally insulated chamber (containing ethanol sus­
paramagnetic materials from ferromagnetic ones is investigated. pension). This chamber was then placed under an AC magnetic field
Furthermore, the comparison of heating of ferromagnetic and super­ (100Oe-100 kHz) and the temperature raising was measured using a
paramagnetic nanoparticles and the role of heating mechanisms in these digital infrared thermometer (AZ Co., Model 8869) at various times. A
materials are carefully studied. All tests are performed on strontium powerful 64-megapixel camera was also used to detect the mass move­
ferrite (SrFe12O19) ceramic nanoparticles as an important case study. ment of nanoparticles inside the chamber (after field application). The
amounts of adsorbed and released drug are monitored as a function of
2. Materials and methods soaking time by UV spectroscopy (UV–Vis spectrophotometer, Optizen
3220) at 235 nm.
2.1. Synthesis and analysis of SrFe12O19 ceramic nanoparticles
2.2. Theoretical concepts
Chemically grade ferric chloride (FeCl3-6H2O), strontium carbonate
(SrCO3), hydrochloric acid (HCl), sodium hydroxide (NaOH), absolute The mechanism by which the change of particle size can affect the
ethanol, Citric acid and sodium citrate were obtained from Merck group magnetic properties of materials is to upset the balance between
(Germany). Commercial cisplatin (CP) was purchased from a pharmacy. anisotropy energy and thermal energy [12]. As a symbol representing
Type-B gelatin with 100–115 mmol of carboxylic acid per 100 g of the change of particle size, a dimensionless σ parameter can be defined
protein and an average molecular weight 40–50 kDa was obtained from by dividing anisotropic energy (KV) by thermal energy (KbT):
Sigma–Aldrich (St. Louis, MO). To synthesize pure SrFe12O19 pure
nanoparticles with a plate-like structure, the co-precipitation method σ=
KV
(1)
was applied. For this purpose, the strontium carbonate was dissolved in kb T
HCl to obtain strontium chloride solution. A ferric chloride (dissolved in
distilled water) and strontium carbonate (dissolved in HCl) solutions where K is anisotropy constant, V is the volume of nanoparticles, Kb is
with 9.23 M ratio of Fe3+/Sr2+ were prepared [19]. Sodium hydroxide the Boltzmann constant and T is the temperature.
(5 M) solution was gradually added to the mixture in order to precipi­ If the nanoparticle size (in a single-domain state) is less than a certain
tation of the ferrite precursors at room temperature at a pH value of 10. limit, the thermal energy (caused by atomic vibrations) overcomes the
To achieve an aqueous suspension with a good homogeneity as well as a anisotropy one (i.e. σ < 1), so the spins will move freely and a super­
stable pH conditions, the stirring process was performed gently for 15 paramagnetic mode will be formed. On the other hand, by increasing the
min. Filtered brown sediments are washed with deionized water and size of nanoparticles (single-domain nanoparticles), the anisotropic en­
dried overnight at 100◦ C. A calcination process with the rate of 10 ◦ C/ ergy overcomes the thermal one (i.e. σ > 1), during which a
min was then performed on the dry precursors for the formation of the
SrFe12O19 phase. The calcination temperatures were set on at 850, 900,
1000 ◦ C with a maintaining time of 2 h.
An ultrasonic bath with a solution of 0.05 mol/L of sodium citrate
and 0.0001 mol/L of citric acid at pH = 7, was used to treat the
SrFe12O19 nanoparticles (MNPs). MNPs were then suspended in citrate/
citric solution under N2(g). After being suspended for 24 h, MNPs were
separated from the supernatant using a magnet and subsequently dried
at 40 ◦ C.
In continue, 5 g of gelatin powder was dissolved in 100 ml of distilled
water and kept at 45–50 ◦ C to completely swell, and then it was stirred at
a speed of 500 rpm to form a homogeneous 5% (g/ml) gelatin solution.
At the next stage, modified MNPs were added in 2% (w/v) ratio to the
formed gelatin solution. The resulting gelatin /MNPs mixture was then
homogenized for 30 min using an ultrasonic bath.
Cisplatin (CP) with a concentration of 1 mg/ml was incorporated
into the gelatin /MNPs mixture with a constant stirring of 1 h. A
relaxation time of 24 h was then considered to absorption of the drug in
hydrogel. For the crosslinking the gelatinous groups, 250 µl 2.5% (g/ml)
glutaraldehyde (GA) solution was added to gelatin /MNPs/CP mixture.
At the final stage, the resultant solution was poured into glass molds Fig. 1. Influence of σ on the superparamagnetic (SP) and ferromagnetic (FM)
for lyophilization. The glass mold samples were frozen at − 80 ◦ C for 2 states. As the anisotropy of the spin becomes dominant (σ > 1), macrospin
days (48 h). The frozen samples were then subjected to lyophilization for becomes bound from free state.

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M. Abdellahi et al. Journal of Magnetism and Magnetic Materials 530 (2021) 167938

ferromagnetic mode will be formed (Fig. 1). Table 1

According to Eq.1, in high values of σ (σ ≫1), the nanoparticles are The crystalline size and magnetic properties of the SrFe12O19 nanopowders at
out of the single-domain mode and thus un-usable in magnetic hyper­ various calcination temperatures.
thermia (Fig. 1). The concepts of free and bounded spin as well as Temperature (◦ C) Crystallite size (nm) Hc (Oe) Ms (emu/gr)
different values of σ, as illustrated in Fig. 1, will be discussed in the 900 99 5121 59
following sections. 1000 121 4399 61

3. Results
Additional VSM analysis is also needed to find the calcination tem­
3.1. Finding the single-domain size of SrF12O19 ceramic nanoparticles perature, beyond which the Srfe12O19 structure is likely to deviate from
the single-domain state. Fig. 3 shows the VSM results for the calcination
According to Fig. 1, it is necessary to find the single-domain size in temperature range 900 to 1000 ◦ C. As can be seen, with the temperature
SrFe12O19 ceramic nanoparticles. If the size range of single-domain rising from 850 to 900 ◦ C, Hc has shown an increasing trend, while
nanoparticles is specified, then by changing their size, their magnetic further increases to 1000 ◦ C, Hc tended to get smaller. To explain this
properties are predictable and also controllable. phenomenon, it must be understood that, increasing nanoparticles size
Fig. 2 shows the documentations of the synthesis SrFe12O19 ceramic as a result of the increasing calcination temperature, causes the increase
phase at two temperatures of 900 and 1000 ◦ C. As the XRD results show of the magnetostatic energy and hence a thermodynamically unstable
(Fig. 2a), the pure of SrFe12O19 ceramic nanoparticles have been syn­ structure. The magnetostatic energy can be reduced by reducing the
thesized at both 900 and 1000 ◦ C calcination temperatures. By external demagnetizing field; one way to do this is to divide a single
increasing calcination temperature to 1000 ◦ C, the sharpening of the domain into multi domains and consequently decreasing Hc [13].
XRD peaks confirms the growth of SrFe12O19 micro and nanostructures. From the above discussion it can be claimed that the maximum size
Furthermore, at 1000 ◦ C (Fig. 2c), the co-precipitated SrFe12O19 ceramic of the single-domain is obtained at the calcination temperature of 900 ◦ C
powders show a plate-like hexagonal shape and a high particle size and with further increase in temperature, nanoparticles with multi-
distribution than that obtained at 900 ◦ C (Fig. 2b). domain structure will be formed. In Table 1, the VSM numerical re­
According to Table 1, the Rietveld method [20] confirms that the sults are presented.
crystalline size of the Srfe12O19 structure has increased from about 100
nm to about 120 nm as a result of the increasing calcination temperature 3.2. σ values at different particle size
from 900 to 1000 ◦ C. These results are in accordance with those reported
by M.M. Hessien et al. [19]. It should be noted that, irregular growth of Fig. 4 shows the PSA analysis results of the SrFe12O19 ceramic
particle size can take the structure of SrFe12O19 ceramic out of the nanopowders. In this figure type D is related to the SrFe12O19 ceramic
single-domain state and practically disrupt its magnetic state. nanopowders synthesized at the calcination temperature of 900 ◦ C. As
previously discussed in section 3–1, due to the maximum size of single-
domain particles (with the mean size of about 99 nm) at 900 ◦ C, the
maximum amount of magnetostatic is created [13]. This causes a ther­
modynamically unstable system with the largest size of macrospin and
hence maximum anisotropy energy (KV). Here, σ takes its largest
amount (σ ≫1).
By a mechanical milling process, nanoparticle size will go through a
downward trend, so that a mean crystalline size of 60 nm is obtained
after 8 h of milling (Fig. 4-type C). In such a case, σ tends to be smaller
values but still larger than one (because the anisotropy energy is still
high and overcomes the thermal energy).
By increasing milling time to 16 h, the size of nanoparticles reaches
28 nm, during which the value of anisotropic energy is approximately
equal to the thermal energy, and the σ reaches one (type B). Further
milling to 22 h, causes the continuation of the particle size reduction

Fig. 2. Documentations of the synthesis pure SrFe12O19, a) XRD results. FESEM Fig. 3. Hysteresis loop of the SrFe12O19 ceramic samples at various calcination
images at calcination temperatures of b) 900 and c) 1000 ◦ C. temperatures.

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M. Abdellahi et al. Journal of Magnetism and Magnetic Materials 530 (2021) 167938

140 Here, it seems the soft-ferromagnetic nanoparticles have a lower heating

potential than superparamagnetic ones.
120
4. Discussions

100
Two mechanisms are very influential in heating potential of nano­
particles under magnetic fields, i.e. Neel and Brownian mechanisms
Size (nm)

80 (Fig. 9). In the Neel mechanism, heat is formed by the rotation of a

macrospin from one easy axis to another [13]. This mechanism is more
60 common in superparamagnetic materials, in which due to the low
anisotropy energy, the spin is free and does not couple with the orbital
(Fig. 1, σ < 1).
40
If the growth of single-domain nanoparticles reaches a point that the
macrospin couples with the orbital (due to the high anisotropic field), a
20 bounded macrospin is formed (Fig. 1, σ > 1). In this case, by applying
the field, the nanoparticles begin to rotate, which is known as the
0 Brownian mechanism.
A B C D According to Fig. 6, single-domain nanoparticles with the largest size
(σ≫1) have the lowest releasing heat under AC magnetic field. The
Fig. 4. PSA analysis of the SrFe12O19 nanoparticles with various values of σ.
reason for this phenomenon is the failure of the Neel and Brownian
mechanisms. In fact, increasing the size of nanoparticles makes the
process, and hence decreasing σ to the values lower than one (type A). applied fields unable to rotate them and also the bounded macrospins.
From Fig. 5a, it is clear that in these nanoparticles, the amount of Hc is
3.3. Magnetic properties of the Srfe12O19 nanoparticles equal to 5000 Oe while the applied fields (in magnetic hyperthermia)
are about 100 to 200 Oe, which are not able to overcome the anisotropy
Fig. 5 shows the magnetic properties of the Srfe12O19 ceramic sam­ and movement of macrospin. The low heat generated in samples with
ples at various values of σ. As can be seen in Fig. 5a, the maximum size of σ≫1 (Fig. 6), is due to the presence of smaller nanoparticles in the
single-domain nanoparticles with a large amount of σ represents structure (Fig. 5a, TEM analysis).
maximum amount of Hc. By decreasing σ values, Hc and Ms start to In the σ values less than one (σ < 1), the nanoparticles are in their
decrease (Fig. 5b-d). This decreasing process will be discussed in Section smallest state [12]. In this case, thermal energy (resulted by atomic vi­
4. brations [13]) prevails over anisotropy as a result of the presence of free
Fig. 5a, b show nanoparticles with hard-ferromagnetic and soft- macrospins. In this case, the Neel mechanism is activated by two driving
ferromagnetic property, respectively. Fig. 5c, represents the equilib­ forces. The first is the heat of the atomic vibrations which causes the
rium between anisotropy energy and thermal energy (σ ≈ 1) and rotation of free macrospins, and the second, applied field, which can
determins the boundary of the ferromagnetic and superparamagnetci rotate the macrospins with a high frequency. In this case, the Brownian
states. Eventually, with excessive particle size reduction and conse­ mechanism will not be active because in single-domain nanoparticles
quently the dominance of thermal energy over anisotropy one, a with a size of about 22 nm (Fig. 4), macrospins are not affected by the
superparamagnetic state will be formed (Fig. 5d) anisotropy of the system and move freely (Fig. 1). This means that there
is no coupling between the spin and the orbital and the nanoparticles
3.4. Magnetic hyperthermia analysis will not rotate.
At the boundary of ferromagnetic and superparamagnetic nano­
Fig. 6 shows the heat released by SrFe12O19 nanoparticles (in a particles (σ≈1), there will be the most heat produced (Fig. 6). It should
toluene suspension) under AC magnetic fields. As can be seen, the be noted that increasing σ , as a result of the nanoparticle volume, causes
samples with maximum size of the single-domain nanoparticles (σ ≫1) two important events. The first event is the reduction of the spin canting
have the lowest releasing heat. On the other hand, the samples with the effect which results in the amplification of the spin rotations in the same
σ values close to one have the maximum amount of heat release. In other direction and hence a higher potential of Neel Mechanism (Fig. 10) [21].
words, it seems that the ferromagnetic samples have a higher potential The second is the growth of the macrospin size which is a leading stage
in releasing heat compared to that of superparamagnetic ones. These to produce more spin torque and hence more heating energy.
results will be discussed in Section 4. At the boundary of the superparamagnetic and ferromagnetic states
(σ≈1), the maximum size of the free macrospin is present1 (Fig. 1). In
3.5. Coating and drug delivery this case, the temperature-induced spin rotation (resulted by the thermal
energy of atomic vibration) stopes and hence the whole of the applied
Fig. 7 shows a schematic view of the coating process of the CP as the field is absorbed by the free macrospin due to the absence of any phase
drug and MNPs as the driving force behind the release of the drug. As degradation. On the other hand, when σ≈1, the spin canting has the
can be seen, a freeze drying process was used to create gelatin magnetic minimal effect on the free-macrospin and hence the maximum state of
scaffolds as carriers of drug. the amplification of the spin rotations in the same direction occurs.
To investigate of the drug release of the scaffold samples, a small According to the above-mentioned discussions, when σ≈1, three
piece of the magnetic scaffold is subjected to the AC magnetic field. Drug factors play the most important role in the activation of Neel mecha­
release rates were expected to be based on the magnetic hyperthermia nism; a) The weakness of spin canting, b) the highest torque of the free
results of the MNPs (Fig. 6). However, the process of drug release does macrospin and c) absorption of the whole of applied frequency by the
not surprisingly follow the expected results (Fig. 8). macrospin.
As can be seen in Fig. 8, MNPs with σ = 1, caused a maximum It should be noted that the thermal energy (resulted by the atomic
amount of drug release which is in accordance of that in magnetic hy­
perthermia analysis (Fig. 6). Although soft-ferromagnetic nanoparticles
(σ > 1) had better releasing heat than superparamagnetic ones (σ < 1) 1
. When σ reaches values higher than one, macrospin will be bounded and
(refer to Fig. 6), the results of drug release are quite the opposite (Fig. 8). cannot rotate freely.

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M. Abdellahi et al. Journal of Magnetism and Magnetic Materials 530 (2021) 167938

(a) 80 (c)
60
60

40
40
Magnetization (emu/g)

Magnetization (emu/g)
20
20

0
0

-20 -20

-40 -40

-60 -60

-15000 -10000 -5000 0 5000 10000 15000 -10000 -5000 0 5000 10000

Applied field (Oe) Applied Field (Oe)

(b) (d)
60 40

30
40
Magnetization (emu/g)

Magnetization (emu/g) 20
20
10

0 0

-10
-20
-20
-40
-30

-60 -40

-10000 -5000 0 5000 10000 -10000 -5000 0 5000 10000

Applied field (Oe) Applied field (Oe)

Fig. 5. VSM and TEM analyses results of the SrFe12O19 ceramic nanoparticles at a) σ ≫1, b) σ > 1, c) σ = 1, d) σ < 1.

vibration) is only active in the range of σ < 12. This activation may have
a negative consequence. In fact, the rotation of the magnetic field-
6 induced spins may not be in-phase with that of atomic vibration-
induced spins. This is why the heating potential of nanoparticles in
5 the range of σ < 1 is less than that of σ≈1.
By increasing σ to the values beyond one (σ > 1), due to the increase
of anisotropy, the spin is unable to move freely and is bounded by the
4 anisotropy of the system (Fig. 1). Here, to rotate the bounded spin, an
operating frequency (by the applied field) is definitely needed. How­
ever, before the start of the spin rotation, one must spend some of this
3
frequency overcoming the anisotropy. This means that not all applied
frequencies are absorbed by the spin for rotation and hence the power of
2 the Neel mechanism is reduced. This causes the reduction of the heating
potential of the nanoparticles under magnetic field. It should be noted
that the effect of Neel mechanism is reduced; however, the Brownian
1
mechanism is activated due to the rotation of the nanoparticles.
Fig. 11 is the processed image of the motion of nanoparticles (in a
0 toluene suspension) under magnetic field in different values of σ. As can
0 20 40 60 80 100 120 be seen, in the hard-ferromagnetic state, where the single-domain
nanoparticles have their largest size (σ≫1), there is the least jump and
t (s)
Fig. 6. Magnetic hyperthermia analysis at various values of σ.
2
. When σ≥1, the anisotropy energy is more than the thermal energy, and
hence thermal energy has not any role in the rotation of the macrospin.

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M. Abdellahi et al. Journal of Magnetism and Magnetic Materials 530 (2021) 167938

Fig. 7. A shematyic view of the coating process and provide magnetic scaffold.

From Fig. 11, it can be observed that in soft-ferromagnetic MNPs (σ

> 1), the mobility of the nanoparticles is at its highest. In this case, the
4 macrospin is not free (refer to Fig. 1), and its coupling with the orbital
causes the nanoparticles to move (Brownian mechanism). Furthermore,
>1 the nanoparticles are smaller in size than those of σ≫1 and therefore
Percent Release (%)

0 5 10 15 20 25
Time (h)

Fig. 8. CP release of gelatin scaffolds containing MNPs with various values of σ.

mobility of the nanoparticles. In fact, the large size of the nanoparticles

in this case makes them difficult to move. This event deactivates the Fig. 10. The effect of the spin canting which results in the amplify of the spin
Brownian mechanism and prevents heat production (refer to Fig. 6). rotations in the same direction.

Fig. 9. A schematic representation of the Neel and Brown mechanism.

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M. Abdellahi et al. Journal of Magnetism and Magnetic Materials 530 (2021) 167938

Distance of nanoparticles from the floor (mm) nanoparticles are placed in a jelly medium. Two factors appear to
impede the rotational motion of the MNPs and consequently the Brow­
0.000 1.000 2.000 3.000 4.000 5.000 nian mechanism. One is the crosslinking between functionalized MNPs
and gelatin groups and the other is the high accumulation of MNPs in the
domains created by GA. As can be seen in Fig. 12, GA which plays the
role of crosslinking between gelatinous groups [22], creates nano-sized
domains with high accumulation of nanoparticles. Some of these do­
mains are showed in Fig. 12. Due to the crosslinking between func­
tionalized MNPs and gelatin groups, the rotation of accumulated MNPs
in these domains is difficult under the applied magnetic field.
Fig. 13 shows the microstructure of the prepared magnetic scaffold
(Fig. 13a) and the corresponded EDX analysis (Fig. 13b). As it is
observable from the EDX analysis, the drug and magnetic nanoparticles
are well distributed on the surface of the gelatin coating. Elemental
mapping image for Fe confirms that gelatinous domains made with GA
also present in the magnetic scaffold. These domains contain accumu­
lated MNPs which are attached to the gelatin shell and cannot freely
rotate. This causes a loss of the Brownian mechanism and consequently
the heating potential of the soft-ferromagnetic nanoparticles.
Fig. 11. Processed image of the mobility of magnetic nanoparticles at various
values of σ.
5. Conclusions
they rotate easily during the field applied. Fig. 11 also confirms that the
In this work, co-precipitation method was used to produce SrFe12O19
Brownian mechanism is an active mechanism in soft-ferromagnetic
nanoparticles. Then different sizes of the SrFe12O19 nanoparticles were
MNPs and the resulting heat shown in Fig. 6 will most likely is due to
obtained using the mechanical milling method. According to results,
the Brownian mechanism.
single-domain nanoparticles with the largest size (σ≫1) have the lowest
According to Fig. 11, at the boundary of ferromagnetic and super­
releasing heat under AC magnetic field. The reason for this phenomenon
paramagnetic states (σ≈1), the mobility of nanoparticles is reduced.
is the failure of the Neel and Brownian mechanisms. In the σ values less
This indicates that the Brownian mechanism is inactive or slightly pre­
than one (σ < 1), the nanoparticles are in their smallest state and the
sent. The reason is clear; at the boundary between ferromagnetic and
thermal energy prevails over anisotropy. In this case only the Neel
superparamagnetic states, the macrospin is still free and absorbs all the
mechanism was active because macrospins were not affected by the
frequency provided by the magnetic fields. This prevents any rotation in
anisotropy of the system and moved freely. At the boundary of ferro­
the nanoparticles themselves. In this case, most of the heat produced is
magnetic and superparamagnetic nanoparticles (σ≈1), there will be the
due to the Neel mechanism.
most heat produced. Three factors including the reduction of the spin
According to Fig. 11, in superparamagnetic materials (σ < 1), the
canting, the growth of the macrospin size and blocking the macrospin
mobility of nanoparticles has almost reached its lowest point. Here, due
were involved in the incident. Although soft-ferromagnetic nano­
to the low anisotropy energy and hence absolute freedom of micro­
particles had better releasing heat than superparamagnetic ones, the
spinthe, Brownian mechanism is completely inactive and the heat
results of drug release in gelatin coated magnetic nanoparticle are quite
generated will be due to the Neel mechanism.
the opposite. This was because of the first, cross-linking between func­
To investigate the failure of the Brownian mechanism in gelatin
tionalized MNPs and gelatin groups and second, nano-sized domains
samples with soft-ferromagnetic core, microstructural analyses can be
with high accumulation of MNPs.
useful. Fig. 12 shows TEM image of the mixture of the gelatin containing
drug and soft-ferromagnetic core. As demonstrated, the magnetic

Fig. 12. TEM images of the mixture of MNPs/CP coated with gelatin layers crosslinked with GA.

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M. Abdellahi et al. Journal of Magnetism and Magnetic Materials 530 (2021) 167938

Fig. 13. The microstructure of the prepared magnetic scaffold (Fig. 13a) and the corresponded EDX (Fig. 13b) and Elemental mapping image for Fe.

Declaration of Competing Interest [11] R.W. Chantrell, J. Popplewell, S.W. Charles, The coercivity of a system of single
domain particles with randomly oriented easy axes and a distribution of particle
size, J. Magn. Magn. Mater. 15-18 (1980) 1123–1124.
The authors declare that they have no known competing financial [12] J. Carrey, B. Mehdaoui, M. Respaud, Simple models for dynamic hysteresis loop
interests or personal relationships that could have appeared to influence calculations of magnetic single-domain nanoparticles: Application to magnetic
the work reported in this paper. hyperthermia optimization, J. Appl. Phys. 109 (2011), 083921.
[13] N. A. Spaldin, Magnetic materials fundamentals and application, Cambridge
University Press, The Edinburgh Building, Cambridge CB2 8RU, UK ATERIALS.
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