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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Core–shell superparamagnetic iron oxide nanoparticle (SPION)

clusters: TEM micrograph analysis, particle design and shape analysis
Lazar Kopanja a,n, Slavko Kralj b, Dragisa Zunic c, Boris Loncar a, Marin Tadic d
a
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, PO Box 3503, 11120 Belgrade, Serbia
b
Department for Materials Synthesis, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia
c
Faculty of Computer Sciences, John Naisbitt University, Bulevar Umetnosti 29, 11070 Belgrade, Serbia
d
Condensed Matter Physics Laboratory, Vinca Institute, University of Belgrade, P.O. Box 522, 11001 Belgrade, Serbia

art ic l e i nf o a b s t r a c t

Article history: For the first time, particle shape analysis of silica coated iron oxide (maghemite/magnetite) nanoparticle
Received 19 March 2016 clusters (core–shell nanostructures) is discussed using computational methods. We analyzed three
Received in revised form samples of core–shell nanostructures synthesized with different thickness of the silica shell. A new
29 March 2016
computational method is presented and successfully applied to the segmentation of the core–shell na-
Accepted 30 March 2016
noparticles, as one of the main problems in image analysis of the TEM micrographs. We have introduced
the “circularity coefficient”, marked with kcirc and defined as the ratio of circularity measure C2(S) of
Keywords: nanoparticles core and circularity measure core–shell nanoparticles in order to answer the question how
Synthesis the shell affects the overall shape of the final core–shell structure, with respect to circularity. More
Superparamagnetism
precisely, the “circularity coefficient” determines whether the circularity of the core–shell nanoparticle is
Magnetic properties
higher, lower or equal to the circularity of the core. We have also determined the shell's share in the
Image analysis
Circularity overall area of the core–shell nanoparticle. The core–shell nanoparticle clusters here investigated exhibit
Shape descriptors superparamagnetic properties at room temperature, thus emphasizing their potential for use in practical
applications such as in biomedical and particle separation. We show that the saturation magnetization
strength can be easily adjusted by controlling the thickness of the silica shell.
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

1. Introduction on the residual oxygen content in the reaction environment [13].

Shape is an important feature of nanoparticles that can be used
to tailor the physical properties of materials, whereas the shape
descriptors are a powerful tool in many image processing tasks. It
is known that different shapes of the nanoparticles have a sig-
nificant impact on their properties [1–4]. As an example we can
mention that the coercitivity dependence on changing the shape
of nanoparticles, where coercivity changes the value up to several
times [5–7]. It has been shown that, by varying the size and shape
as well as core–shell structures of the nanoparticles their physical
properties can be adjusted in a wide range [2,8–10].
Over the past few years, shapes of ordinary nanoparticles have
been analyzed in the literature [11–16]. It have been presented a
characterization of nanoparticles by using two different forms of
circularity measure and results were obtained using MATLAB
software package [12]. An advanced version of the thermal
decomposition of acetylacetonate precursors was developed to
prepare cobalt ferrite nanoparticles, introducing a rigorous control
n
Corresponding author.
E-mail address: kopanjal@yahoo.com (L. Kopanja).
This new concept derived from the statistical analysis of S(T)EM
(scanning transmission electron microscopy) images, while for
particle shape evaluation a standard measure of circularity calcu-
lated using the software “Fiji” was applied.
Recently, several groups have reported interesting core–shell
structures where the nanostructures consist of a different core and
shell materials [17–21]. There is an increase in the number of re-
search papers on the topic of core–shell structure published over
the last 10 years as illustrated in Fig. 1.
The superparamagnetic iron oxide nanoparticles (SPION),
which may exhibit interesting effects and have potential applica-
tions in various areas as multi-function materials, have attracted
considerable attention for both fundamental and technological
interest [22]. Nanosized maghemite and magnetite are ferrimag-
netic materials that are used for various biomedical applications
(targeted drug delivery, tissue engineering, local hyperthermia,
ferrofluids, contrast agents in nuclear magnetic resonance ima-
ging, magnetic separation, etc) due to its biocompatibility, non-
toxicity, sufficiently high magnetic moments, room-temperature
superparamagnetism and easy and economical synthesis of these
materials [22–27]. The increased demands from different biome-
dical applications have led to novel nanoparticle designs and the

http://dx.doi.org/10.1016/j.ceramint.2016.03.235
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: L. Kopanja, et al., Core–shell superparamagnetic iron oxide nanoparticle (SPION) clusters: TEM micrograph
analysis, particle design and shape analysis, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.235i
2 L. Kopanja et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

the particle shapes. Moreover, in the literature, a rough char-

Fig. 1. Published articles in the period from 2006 to 2015 using keywords “core
shell nanoparticles” (data taken from citation database Scopus).
development of various kinds of magnetic composites, ferromag-
netic 3D-metal oxide materials [28]. In particular, the preparation
of different core–shell magnetic composite nanostructures has
recently been reported, leading to novel and improved magnetic
properties for these materials [28–29].
Recent methods for the synthesis allow the synthesis of not
only symmetrical (spherical) shape of core–shell nanostructures,
but also a number of other shapes such as disks, cubes, rods, tubes,
hexagonal, prism, octahedron and others [30–35]. Fig. 2 shows a
different class of core–shell nanoparticles presented in [36].
A number of studies on the synthesis of nanoparticles is cur-
rently dealing with controlled synthesis of new morphologies,
including core–shell structures, which show interesting properties
and are expected to show new physical properties useful in
medicine, pharmacy, catalysis, sensors, media storage, etc. [37–43].
Pichon et al. [44] examined structure, morphology and composi-
tion of the cubic core–shell nanoparticles and compared this with
spherical nanoparticles. Sacanna et al. [45] investigated the role of
shape in colloidal self-assembly and argues for the importance of a
tight synergy between particle design and assembly strategies.
All the aforementioned references lack a unique description of
acterization of nanoparticle's shape such as “core–shell structure”
[17,39], “core–shell nanoparticles” [21,44], “spherical in shape”
[46], “almost spherical shaped nanoparticles” [47], “near spherical”
[48], “spherical shape” [49] etc. is often used.
Therefore, in the previously reported literature there is a lack of
detailed shape analysis of core and shell parts that is important for
better control of core–shell nanoparticle properties. In this paper
we give a new approach to the analysis of spherical core–shell
nanoparticles using a measure of circularity (roundness). The cir-
cularity measure is feature of shape that defines the degree to
which a shape differs from a perfect circle. The newly proposed
measure is a number from (0,1] and reaches a value of 1 only in the
case of the perfect circle. The basic purpose of introducing circu-
larity measures as a shape descriptor is obtaining able to nu-
merically describe the shapes of nanoparticles and providing their
differentiation.
2. Materials and methods
2.1. Synthesis
The core–shell particles, namely superparamagnetic nano-
particle clusters (MNCs), were kindly provided by Nanos SCI
(www.nanos-sci.com) commercially available under the
“iNANOvative™|BIO” trademark. These MNCs were synthesized by
a self-assembly of primary maghemite nanoparticles followed by
coating of nanoparticle clusters with a layer of silica. We have
synthesized three samples of core–shell nanostructures with dif-
ferent thickness of the silica shell (MNC1-thick silica shell, MNC2-
medium silica shell and MNC3-thin silica shell. The detailed pro-
cedures were described in our previous publications [50–53]. First,
single maghemite (γ-Fe2O3) nanoparticles were synthesized using
precipitation from an aqueous solution [51]. Further synthesis
steps based on the assembly of maghemite (γ-Fe2O3) nano-
particles with specially adjusted surface properties into the

Fig. 2. Different classes of core–shell nanoparticles of: (a) spherical core–shell nanoparticle; (b) hexagonal core–shell nanoparticles; (c) nanoparticle clusters coated by single
shell material; (d) “nanomatryushka” material; (e) movable core within hollow shell material [36].

Please cite this article as: L. Kopanja, et al., Core–shell superparamagnetic iron oxide nanoparticle (SPION) clusters: TEM micrograph
analysis, particle design and shape analysis, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.235i
 L. Kopanja et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎
clusters in an emulsion system. The procedures were described in
our previous publications [52,53]. The precise control of the MNC
size is finally achieved using a high-gradient magnetic separator
(HGMS). The synthesis procedures were developed exclusively by
Nanos SCI and are suitably protected.
2.2. Circularity measure
Shape descriptors and corresponding measures quantitatively
describe the shapes of particles. In this paper the shape of core–
shell nanoparticles is analyzed using circularity measure. Circu-
larity (roundness) is one of the main shape descriptors discussed
in the literature [13,54–59]. The aim of this measure is to answer
the question of how the shape differs from an ideal circle. Circu-
larity measure ranges over the interval (0,1] and gives the mea-
sured circularity equal to 1 if and only if the measured shape is a
circle. Circularity is usually defined as the relationship between
the shape area and its perimeter [4,12,13,15,60–62]:
4⋅π⋅A
C1 (S ) =
P2
where A represents the shape's area and P is the shape's perimeter.
Circularity measure C1(S) has several desirable properties:

C1(S) ϵ(0, 1] for all shape S,

C1(S) ¼1 ⇔ S is a circle,

C1(S) is invariant with respect to similarity transformations
(translations, rotation and scaling).
The disadvantages of standard circularity measure C1(S) are
discussed in the literature [12,54]. In fact, considering that this
measure circularity depends on the perimeter of the observed
shape, the image quality and the applied resolution substantially
affect the application of measure C1(S). In the presence of noise as
well as of narrow protrusions there is a big difference between the
results, because then there is a large increase in the length of the
perimeter of particles, and the measured circularity using measure
C1(S) decreases significantly. For these reasons, we used circularity
measure based on a calculation of the area in which there is no
need to calculate the perimeter. Geometric moments mp, q (S ) for
given shape S are defined as:
mp, q (S ) = ∬S xp⋅yq dxdy.
Geometric moments mp, q (S ), in the case of digital objects that
are a digitization of real shapes, are substituted by their discrete
analogue in the following way:
mp, q (S ) ≈ ∑ i p⋅j q
(i, j)∈ S ∩ Ζ 2
As the moments mp, q (S ) are not invariant with respect to
translation (translation of shape changes the values of moments),
it is desirable to calculate central geometric moments mp, q (S )
which are defined as
mp, q (S ) = ∬S ( x − xc (S) )p⋅( y − yc (S) )qdxdy
where the centroid (xc (S ) , yc (S )) of the shape S is given by
⎛m (S ) m0,1 (S ) ⎞
( x c (S ), yc (S ) ) = ⎜ m1,0 (S ) , ⎟.
⎝ 0,0 m0,0 (S ) ⎠
The moments mp, q (S ) are invariant with respect to translation,
but they change under scaling, so it is preferred to use the so-
called normalized moments μp, q (S ) defined by
Please cite this article as: L. Kopanja, et al., Core–shell superparamagnetic iron oxide nanoparticle (SPION) clusters: TEM micrograph
analysis, particle design and shape analysis, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.235i
3
mp, q (S )
μ p, q (S ) =
p +q
m0,0 (S )1 + 2 (6)
In Ref. [63], Hu has introduced a series of so-called algebraic
invariants. Zunic et al. [54] have shown that the Hu moment
(m2,0 (S ) + m0,2 (S )) /(m0,0 (S ))2 reaches the minimum value of 1/(2π)
if and only if S is a circle. Based on that result, definition of cir-
cularity measures is presented based on the calculation of area.
Definition 1. Let S be an arbitrary shape whose centroid coincides
with the origin. Then circularity C2(S) is defined as:
1
C2 (S ) =
(
2π μ2,0 (S ) + μ 0,2 (S ) ) (7)
Circularity measures C2(S) has desirable properties, just like the
measure C1(S), and satisfies the conditions that we previously
mentioned. This measure is based on standard algebraic opera-
tions, which makes an implementation rather simple and
straightforward.
(1)
2.3. Image segmentation of core–shell nanoparticles
This work studies images of silica coated iron oxide core–shell
nanoparticle clusters with sizes of about 100 nm. On these mi-
crograph images, core–shell nanoparticles are not clearly sepa-
rated from the background and other particles, and image seg-
mentation was the first step in the shape analysis [4,64–67]. Image
segmentation involves the division of images into classes (seg-
ments) with similar characteristics. In the process of segmentation
the most commonly used attribute is illumination (for mono-
chrome images) or colors (for color images). Besides that, other
attributes such as edges, textures, etc., can be used. In the case of
core–shell nanoparticles we suggest the use of image segmenta-
tion with two thresholds which separates the image into three
segments: background, shell and core of nanoparticles.
During image segmentation new software package MIPAR™
(Materials Processing and Automated Image Reconstruction) based
on MATLAB was used [68]. In the process of image segmentation,
this environment provides an opportunity to develop a series of
steps, called a “recipe”. An algorithm (recipe) that is applied to the
images consists of the following steps. The first step is to apply
“Flatten Background” which helps remove brightness gradient by
(2) applying a Gaussian blur. The core–shell nanoparticles were ob-
tained by binary image segmentation using the “Global-Value
Threshold”. It selects pixels as black or white based on whether
they are below or above a certain pixel value. Separating slightly
related image objects was done using the watershed algorithm.
Nanoparticles that are not completely on the image or are over-
(3) lapping with other nanoparticles are removed. Further, the cores
of nanoparticles are obtained by binary image segmentation using
a “Local Threshold” option. It selects pixels as black if they meet
the specified criteria (“Difference Below” mode). After that, when
the core is isolated, the image is corrected by using a series of
erosion, dilation and smoothing steps. In this way, the “holes” on
the inside of nanoparticles are filled. Boundary of nanoparticles is
(4) manually reviewed to determine the accuracy of the obtained
bounds. A similar segmentation procedure is described in [69]. The
images, obtained in segmentation process by applying MIPAR, are
used in the program MATLAB to calculate the described circularity
(5) measure C2(S) for core–shell nanoparticles.
3. Results and discussion
In order to illustrate an application of the proposed procedure
4 L. Kopanja et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

Fig. 3. (a) TEM image of the core–shell nanoparticles with thick shell thickness nanoparticles (MNC1); (b) result of described segmentation procedure of the image a;
(c) isolated entire core–shell nanoparticles from b; (d) Isolated entire core–shell nanoparticles from b.

Fig. 4. (a) TEM image of core–shell nanoparticles with medium shell thickness (MNC2); (b) result of described segmentation procedure of the image a; (c) Isolated entire
core–shell nanoparticles from b; (d) isolated entire core–shell nanoparticles from b.

for image segmentation and analysis using circularity measure C2 5a) is analyzed. We examined only nanoparticles which are com-
(S), in this paper the shape of three groups of the core–shell na- pletely in the image and, for the sake of simplicity, have no in-
noparticles, which differs in the shell thickness (Figs. 3a, 4a and tersections with the other particles. In Figs. 3a, 4a, and 5a there are

Please cite this article as: L. Kopanja, et al., Core–shell superparamagnetic iron oxide nanoparticle (SPION) clusters: TEM micrograph
analysis, particle design and shape analysis, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.235i
 L. Kopanja et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 5

Fig. 5. (a) TEM image of core–shell with thin shell thickness nanoparticles (MNC3); (b) result of described segmentation procedure of the image a; (c) isolated entire core–
shell nanoparticles from b; (d) Isolated entire core–shell nanoparticles from b.

Table 1 Table 2
Results measuring the circularity for Fig. 3b; C2(core–shell)-circularity values of Results measuring the circularity for Fig. 4b; C2(core–shell)-circularity values of
core–shell nanoparticles from Fig. 3c; C2(core)-circularity values of corresponding core–shell nanoparticles from Fig. 4c; C2(core)-circularity values of corresponding
nanoparticle's cores from Fig. 3d and kcirc-corresponding circularity coefficients. nanoparticle's cores from Fig. 4d and kcirc-corresponding circularity coefficients.

Particle's number C2(core–shell) C2(core) kcirc Particle's number C2(core–shell) C2(core) kcirc

No.1 0.9987 0.9980 0.9993 No.1 0.9825 0.9859 1.0035

No.2 0.9988 0.9965 0.9977 No.2 0.9961 0.9895 0.9934
No.3 0.9988 0.9958 0.9970 No.3 0.9943 0.991 0.9967
No.4 0.9954 0.9833 0.9878 No.4 0.9932 0.9846 0.9913
No.5 0.9985 0.9963 0.9978 No.5 0.9947 0.9923 0.9976
No.6 0.9980 0.9975 0.9995 No.6 0.9931 0.9689 0.9756
No.7 0.9957 0.9947 0.9990 No.7 0.9928 0.9899 0.9971
No.8 0.9988 0.9920 0.9932 No.8 0.9891 0.9903 1.0012
No.9 0.9875 0.9855 0.9980 No.9 0.9951 0.9897 0.9946
No.10 0.9980 0.9926 0.9946 No.10 0.9787 0.964 0.9850
No.11 0.9987 0.9941 0.9954 No.11 0.9857 0.9916 1.0060
No.12 0.9978 0.9888 0.9910 No.12 0.9877 0.9965 1.0089
No.13 0.9986 0.9947 0.9961 No.13 0.9872 0.9855 0.9983
No.14 0.9944 0.9894 0.9950 No.14 0.9982 0.9748 0.9766
No.15 0.9967 0.9936 0.9969
No.16 0.9934 0.9873 0.9939
14, 26 and 17 of these nanoparticles, respectively. Figs. 3b, 4b and No.17 0.9864 0.9872 1.0008
No.18 0.9972 0.9834 0.9862
5b show the results of the segmentation algorithm described in
No.19 0.9923 0.9853 0.9929
Section 2.3, which is applied to the core–shell nanoparticles of No.20 0.9944 0.9936 0.9992
Figs. 3a, 4a and 5a, respectively. Images that we get in that way are No.21 0.9907 0.9934 1.0027
divided into three classes: core, shell and background. Images of No.22 0.9947 0.9801 0.9853
No.23 0.9930 0.9941 1.0011
complete core–shell nanoparticles are shown in Figs. 3c, 4c and 5c,
No.24 0.9968 0.9965 0.9997
whereas the corresponding isolated cores are presented on No.25 0.9920 0.987 0.9950
Figs. 3d, 4d and 5d. Each of the core–shell nanoparticles and their No.26 0.9949 0.9828 0.9878
cores are denoted with numbers (Figs. 3c and d, 4c and d and 5c
and d). These images are used in the program MATLAB to calculate
the described circularity measure C2(S). These values are presented individual nanoparticles differ. In all of the observed nanoparticles
in Tables 1–3. Values of circularity closer to 1 indicate that the with the thickest shell (Fig. 3b) circularity of the entire core–shell
particle shape is close to a perfect circle. nanoparticles is greater than the circularity of the corresponding
As can be seen from Figs. 3–5 and from the measured circu- core, while in the other two groups (Figs. 4b and 5b) there are
larity from Table 1–3, shapes of the core of the final structure of nanoparticles which have become less circular after coating. For

Please cite this article as: L. Kopanja, et al., Core–shell superparamagnetic iron oxide nanoparticle (SPION) clusters: TEM micrograph
analysis, particle design and shape analysis, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.235i
6 L. Kopanja et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

Table 3 Table 4
Results measuring the circularity for Fig. 5b; C2(core–shell)-circularity values of Overview analysis results for three groups of core–shell nanoparticles.
core–shell nanoparticles from Fig. 5c; C2(core)-circularity values of corresponding
nanoparticle's cores from Fig. 5d and kcirc-corresponding circularity coefficients. Sample Fig. 3b Fig. 4b Fig. 5b
(thick (medium (thin shell)
Particle's number C2(core–shell) C2(core) kcirc shell) shell)

No.1 0.9939 0.9950 1.0011 Average ratio of core area in core–shell 28.26% 51.19% 63.59%
No.2 0.9962 0.9940 0.9978 nanoparticle area (%)
No.3 0.9908 0.9865 0.9957 Average ratio of shell area in core–shell 71.74% 48.81% 36.41%
No.4 0.9959 0.9954 0.9995 nanoparticle area (%)
No.5 0.9939 0.9947 1.0007 Average circularity measure C2(S) of 0.9970 0.9920 0.9944
No.6 0.9938 0.9939 1.0001 final core–shell structure
No.7 0.9972 0.9984 1.0012 Average circularity measure C2(S) of 0.9928 0.9869 0.9938
No.8 0.9879 0.9839 0.9959 core
No.9 0.9946 0.9934 0.9988 Average circularity coefficient kcirc 0.9958 0.9949 0.9994
No.10 0.9960 0.9957 0.9997 0.0042 0.0051 0.0006
|1−kcirc |
No.11 0.9912 0.9928 1.0017
Number of nanoparticles where the 0 7 7
No.12 0.9968 0.9947 0.9979
cores have higher circularity than
No.13 0.9977 0.9974 0.9997
entire core–shell particle
No.14 0.9962 0.9945 0.9983
Number of nanoparticles where the 14 19 10
No.15 0.9925 0.9939 1.0013
cores have lower circularity than
No.16 0.9948 0.9968 1.0020
entire core–shell particle
No.17 0.9953 0.9941 0.9988

example, the core–shell nanoparticle No. 18 from Fig. 4c is more

circular than its core (Fig. 4d). On the other hand, the nanoparticle
No. 21 from Fig. 4c and d is an example of particles where the
situation is reversed, i.e. where the core is more circular than final
structure. In this regard, in order to quantify the influence of
coating on the circularity of nanoparticles, we introduce a new
term: “circularity coefficient”, denoted by kcirc, defined as the ratio
of circularity of nanoparticles core and circularity core–shell na-
noparticles:
k circ = C2 (core)/C2 (core_shell). (8)

The value of circularity coefficient kcirc answers the question

how the shell influences the shape of nanoparticles, or whether
the circularity of the entire core–shell nanoparticles are higher,
lower or equal to the circularity of the core. The value of the cir-
cularity coefficient greater than 1 (kcirc 41) indicates that the core
has a shape which is closer to a circle. In the case when this
number is less than 1 (kcirc o1) we can conclude that nanoparti-
cle's shell contributed in a direction of higher circularity of that
nanoparticle. If the coefficient kcirc is equal to the number 1, we can
say that the core and the entire nanoparticle are equally circular.
From this it follows that the larger value of |1-kcirc| means greater
shell influence on the circularity of the core–shell nanoparticles.
Further, let kcirc denote the average circularity coefficient of
∑n (i )
i = 1 k circ
nanoparticles sample, which is defined by kcirc = n
where n is
(i )
the number of observed nanoparticles and kcirc is the coefficient
circularity of the particle i of the sample (i¼1,2, …, n). Then the
number 1−kcirc represents the measure of the shell impact on the
Fig. 6. The average ratio of the core and the shell area of observed nanoparticles
from Figs. 3a, 4a and 5a.
Fig. 7. Circularity coefficients of the core–shell nanoparticles by the groups from
Figs. 3b, 4b and 5b.
computed circularity of core–shell nanoparticles where higher
values mean greater influence on the shape. The values of circu-
larity coefficients observed on core–shell nanoparticles of Figs. 3–5
are given in Table 1–3, respectively.
Fig. 6 shows the average ratio of the core and the shell area of
observed nanoparticles from Figs. 3a, 4a and 5a. It can be observed
here that the thickest shell is in Fig. 3a while the less thick is in
Fig. 5a.
Further, in Table 4 the average values of circularity measure C2
(S) for the cores and the final core–shell structures are given. It is
presented that the average circularity coefficient investigated
groups kcirc , measure the impact of shell on the nanoparticles
circularity investigated group |1−kcirc | and the number of nano-
particles where the core is more circular then the final core–shell
structure, and vice versa. Table 4 presents average share of the
core and the shell in the area of the core–shell nanoparticles of
each group.
It can be seen from Table 4 that the average circularity of the
core is less than the average circularity of the final core–shell
structure in all observed groups of nanoparticles. This means that
the shell influenced on the increase of circularity in all three
groups ( kcirc <1). The results show that the lowest shell effect on
the shape of the final core–shell structure is in the case of the third
group (Fig. 5b)) where the shell is the thinnest (| 1−kcirc |=0. 0006).
Fig. 7 shows the circularity coefficients kcirc of individual core–
shell nanoparticles investigated groups from Figs. 3b, 4b and 5b.
Nanoparticles are sorted by the circularity coefficient kcirc in

Please cite this article as: L. Kopanja, et al., Core–shell superparamagnetic iron oxide nanoparticle (SPION) clusters: TEM micrograph
analysis, particle design and shape analysis, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.235i
 L. Kopanja et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎
Fig. 8. Hysteresis loops of the iron oxide nanoparticle clusters with different silica
thickness.
ascending order. On the x-axis ordinal numbers after sorting par-
ticles are shown, while on the y-axis the corresponding circularity
coefficients are shown. The chart in Fig. 7 and the values from the
last two rows of Table 4 show that with increasing the share of the
shell area in the area of the final core–shell nanoparticles (i.e. by
increasing the average shell thickness of the group of nano-
particles) is growing and the relative number of particles within
the group in which the final core–shell structure is more circular
than the core. Namely, the group of the nanoparticles with the
thinnest shell (Fig. 5b) has the 36.41% share of the shell area in the
area of the final nanoparticles. For the most part (58.82%) of these
nanoparticles, the final core–shell structure is more circular than
corresponding core. Further, in the group with a medium thickness
of shell (Fig. 4b), the share of the shell area in the area of the final
core–shell nanoparticles is 48.81%. In almost three quarters of
these nanoparticles the final nanostructures are more circular than
their shells (73.08%). Finally, the core–shell nanoparticles with the
thickest shell (Fig. 3b), the share of the shell area in the area of the
final nanoparticles is 71.74%. For all of these 14 nanoparticles the
final core–shell structure is more circular than corresponding core
(100%).
Presented results open a new way in a unique analysis of the
core–shell structures’ shapes and their correlation with the phy-
sical properties of materials. It should also be noted that the ideal
way of capturing images would be to randomly select a large
number of image regions with no overlap of nanoparticles. In-
vestigation of the structures and shapes of new materials can be
provided using the methods described in this work.
Magnetic properties of the samples have been measured at a
room temperature by VSM showing superparamagnetic features.
Variation of the magnetization values is obtained with the change
of the silica thickness, as shown in Fig. 8. Saturation magnetization
MS decreases significantly with the increasing thickness, as ex-
pected, due to the increasing content of the non-magnetic silica in
the total mass of the measured material. The saturation magneti-
zation observed at the same external field (H ¼1000 Oe) for the
samples is 45.1 (MNC3), 32.4 (MNC2) and 23.2 emu/g (MNC1). So,
the magnetic behavior of the silica coated iron oxide nanoparticle
clusters (core–shell structure) strongly depends on the variation of
the silica shell thickness (silica content). Similar behavior was also
observed in magnetic nanoparticle/silica nanostructures [70–73].
4. Conclusions
Preparation of controllable core–shell structures strongly in-
fluences the physical characteristics of nanomaterials. We show
Please cite this article as: L. Kopanja, et al., Core–shell superparamagnetic iron oxide nanoparticle (SPION) clusters: TEM micrograph
analysis, particle design and shape analysis, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.03.235i
7
that the shape and saturation magnetization strength of super-
paramagnetic iron oxide nanoparticle clusters (core–shell nanos-
tructure) can be adjusted by controlling the thickness of the silica
shell. Therefore it is important to have a method which quanti-
tatively describes the structure and shapes of such nanoparticle
structures, as accurately as possible. We have proposed appro-
priate image segmentation with two thresholds which separates
the image into three segments: background, shell and core of
nanoparticles. Following that, we have used the circularity mea-
sure C2(S), which is based on the calculation of particle's area, for
the shape analysis of the core–shell nanoparticles. Theoretical
foundations and basic properties of C2(S) are presented in detail.
This measure is theoretically well founded and its behavior can be
predicted to some extent. It is a significant property when
choosing the tools for tasks related to the shape analysis of na-
noparticles. In order to compare the shape of the core and the final
core–shell nanoparticle, a new quantity named “circularity coeffi-
cient”, has been defined and denoted with kcirc. In the case when
kcirc o1, we conclude that the nanoparticle's shell approaches the
ideal circle, while in the case when kcirc 4 1, we witness the re-
duction of circularity going towards the shell. The experimental
results show that the shell contributes to the circularity increase of
the final core–shell nanoparticle. Thus, the average circularity
coefficients point to more circular final core–shell structure when
compared to the core. This procedure can be used for detailed
structural and shape analysis of the particles during different
stages in the synthesis process helping to improve quality of final
products. The presented procedure can also be used to study and
better understand the effects of shapes and core–shell structures
on the physical characteristics of the core–shell nanomaterials,
extending their potential practical applications. We have also de-
termined the share of the shell in an overall area of the core–shell
nanoparticle, as an important characteristic of core–shell nanos-
tructures. In short, the suggested procedure can provide the
foundations for further analysis of various structures of materials.
Acknowledgments
The Ministry of Education and Science of the Republic of Serbia
supported this work financially (Grant no. III 45015 and Project no.
174026). D. Žunić wishes to thank V. Dmitrasinović for his help
with English.
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