Acta Materialia 172 (2019) 84e91

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Acta Materialia
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / lo c a t e / a c t a m a t

Full length article

Incorporation of Sc into the structure of barium-hexaferrite nanoplatelets and its

extraordinary finite-size effect on the magnetic properties

a, * b c a, d a, d
Darko Makovec , Matej Komelj , Goran Drazic , Blaz Belec , Tanja Gorsak , Saso
a a, d
Gyergyek , Darja Lisjak
aDepartment for Materials Synthesis, Jozef Stefan Institute, Jamova 39, SI-1000, Ljubljana, Slovenia
b Department for Nanostructured Materials, Jozef Stefan Institute, Jamova 39, SI-1000, Ljubljana, Slovenia
c Department for Materials Chemistry, National Institute of Chemistry, Hajdrihova 19, SI-1000, Ljubljana, Slovenia
d Jozef Stefan International Postgraduate School, Jamova 39, SI-1000, Ljubljana, Slovenia

article info abstract

Article history: In this investigation we analyze an unprecedented difference in the behavior of nanoparticles when compared to the
Received 30 January 2019 corresponding bulk. We have found that a chemical substitution can have the opposite effect on the magnetic properties of
Received in revised form nanoparticles compared to the bulk, as revealed for the first time in the case of Sc-substituted barium-hexaferrite nanoplatelets.
23 April 2019 Even though the Sc substitution is known to greatly decrease the saturation magnetization, M S, of the bulk barium hexaferrite,
Accepted 24 April 2019
Available online 27 April 2019 it showed the opposite effect for nanoplatelets. The M S values of the nanoplatelets (in average 50 nm wide and approximately
2 2
3 nm thick) increased to over 38 Am /kg, compared to ~16 Am /kg for unsubstituted nanoplatelets of comparable average
Keywords: size. The Sc incorporation was investigated with a combination of atomic-resolution imaging and elemental mappings in a
3þ
Nanoparticles scanning-transmission electron microscope. As in the bulk, the Sc ions showed a clear preference for incorporation into an
Magnetic properties * * 2-
R block of the hexaferrite SRS R structure for the nanoplatelets (R and S represent a hexagonal (BaFe6O11) and a cubic
Size effect
2þ
Structure properties relationship (Fe6O8) structural block, respectively). A clear difference between the nano and the bulk observed for the first time was in
Ferrite 3þ 2þ
the partial substitution of the Sc for the Ba in the nanoplatelets; however, this cannot explain the large increase in M S. Ab-
initio calculations suggest that the opposite effect of the Sc substitution in the nanoplatelets to that in the bulk can be ascribed
to specific, two-dimensional magnetic ordering in the platelets.

© 2019 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction nanomaterials indirectly, through the influence on their structure and/or

composition [3,4].
The origin of finite-size effects that make the properties of nanomaterials In this contribution we present another extraordinary result of the finite-
different from the properties of their bulk counter-parts comes either from 3þ
size effect that has not been studied before. We show that Sc -incorporation
their large surface-to-volume ratio or directly from their finite size, i.e., spatial
into barium-hexaferrite structure has the opposite effect on the M S of
confinement. In the domain of magnetic materials, surface spin canting, which 3þ
nanoplatelets to that in the bulk. The Sc substitution in barium hexaferrite
lowers the saturation magnetization, MS, of magnetic nanoparticles can be
attributed to the large surface-to-volume ratio, whereas super-paramagnetism (BaFe12O 19) has been traditionally used to tune the microwave magnetic
is a direct consequence of the finite size [1,2]. Additionally, the small size can properties (i.e., ferromagnetic-resonance linewidth and frequency) of the
3þ
affect the properties of ceramics [5]. Since the substituting diamagnetic Sc ions dilute the mag-
3þ
netic Fe ions, this lowers the M S of the hexaferrite [5,6]. However, when
3þ 3þ
the Sc ions substitute the Fe ions in the hexaferrite synthesized in the
form of thin platelet nanoparticles, i.e., nano-platelets, the effect of the Sc
substitution on the magnetic proper-ties is just the opposite: the Sc-
* Corresponding author.
incorporation strongly increases the
E-mail address: darko.makovec@ijs.si (D. Makovec).

https://doi.org/10.1016/j.actamat.2019.04.050
1359-6454/© 2019 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
D. Makovec et al. / Acta Materialia 172 (2019) 84e91
MS [7,8]. The nanoplatelets of Sc-substituted hexaferrite, approxi-mately 50
nm wide and only 3 nm thick, display an applicable M S exceeding 30
2
Am /kg, whereas the M S of the unsubstituted nano-platelets is much lower,
2
around 15 Am /kg [7,8].
With the improved MS the Sc-substituted barium-hexaferrite nanoplatelets
have demonstrated huge potential with respect to innovative applications.
They exhibit a uniaxial magnetic anisot-ropy, with the easy axis perpendicular
to the platelet, which is a crucial property for the effective alignment of the
dispersed nanoplatelets in an applied magnetic field. Due to high magneto-
4 3
crystalline anisotropy of the hexaferrite (K i ¼ 3.3 x 10 J/m ) [9] the
nanoplatelet subjected to a magnetic field will more easily rotate so as to align
the direction of its magnetic moment with the applied field, rather than
reversing the magnetic moment. Aligning of the nanoplatelet with the field
can be used to transfer torque to its surroundings, as a basis for the
development of many new appli-cations. For example, the magneto-
mechanical actuation of nano-particles in a low-frequency alternating
magnetic field can be used for diverse biomedical applications, ranging from
the remote con-trol of drug-delivery systems to the eradication of cancer cells
[10e15]. Sc-substituted barium-hexaferrite nanoplatelets were also used for
the development of novel, magnetically responsive ma-terials [16e24]. The
first ferromagnetic fluids, i.e., liquids exhibiting a spontaneous magnetic
ordering, in contrast to well-known superparamagnetic ferrofluids, were
prepared by dispersing nanoplatelets in liquid crystals [16]. The suspensions
of nano-platelets in liquid crystals also display strong magneto-electric
[16,17] and magneto-viscous properties [17,18]. Ferromagnetic ordering was
also achieved in concentrated suspensions of nano-platelets in isotropic
liquids. Such suspensions spontaneously form an equilibrium nematic liquid-
crystal phase that is highly sensitive to a magnetic field, even to the Earth's
magnetic field [19]. The suspensions of hexaferrite platelets also show an
extraordinary linear dichroism effect under an applied magnetic field [20,21].
Magneto-optical composites were obtained by the incorporation of
nanoplatelets into a transparent solid polymer matrix [22]. More-over,
magnetically oriented films were prepared by the deposition of hexaferrite
nanoplatelets from their suspensions under an electric or magnetic field for
applications in self-biased nonrecip-rocal devices [23,24].
The hydrothermal method proved to be the most efficient and low-cost
way for the synthesis of hexaferrite nanoplatelets [7,8,25e31]. The
hydrothermal treatment of an aqueous suspension of barium and iron
hydroxides in the presence of a high concen-tration of hydroxyl ions results in
the formation of hexaferrite at relatively low temperatures, below 80 C
[25,26]. Initially, ultrafine, less-than-20-nm-wide, discoid nanoplatelets with
weak magnetic properties are formed. The nanoplatelets with applicable
magnetic properties evolve with exaggerated growth at temperatures above
approximately 150 C; however, the platelets quickly grow to several hundred
nm wide [25,26]. This exaggerated growth can be
3þ
suppressed by using special surfactants [26] or partial substitution of Sc for
3þ
Fe [7,8].
Barium hexaferrite crystalizes in a magnetoplumbite structure, which can
be represented as a hexagonal structure of two alter-nating structural blocks
2-
stacked along the c-direction: a hexagonal “R” block ((BaFe6O11) ) and a
2þ
cubic “S” block ((Fe6O8) ) [9]. The unit cell (S.G.: P63/mmc, a ¼ 0.588 nm,
* *
c ¼ 2.318 nm) can be illus-trated by the RSR S stacking sequence, where the
0 using a TEM (Jeol 2010F) and a C S-probe corrected STEM (Jeol ARM
asterisk denotes the rotation of the block by 180 around the hexagonal c-
2þ
axis. The Ba ions are situated in the middle of the R block, while the Fe
ions occupy five different crystallographic sites, i.e., one tetrahedral (4f 1),
three octahedral (12k, 2a, 4f2), and one trigonal (2b) (Fig. 1(a)). The magnetic
3þ
moments of the Fe ions in the 12k, 2b and 2a sites are aligned parallel to
the c-axis, while the magnetic moments of
the 4f1 and 4f2 sites are antiparallel to the c-axis, resulting in a net magnetic
moment of 20 mB per formula unit at 0 K [9].
The increase of the hexaferrite nanoplatelets’ MS with the incorporation of
the diamagnetic Sc
3þ
is unexpected as the Sc
3þ
substitution in the bulk
hexaferrite results in a decrease of the M S and a gradual change of the
3þ
hysteresis loop from hard-to soft-magnetic [5,6,32]. The Sc ions are larger
3þ
(0.745 Å for the coordi-nation number CN¼VI) than the Fe ions (0.55 Å
2þ
for CN¼VI), but smaller than the Ba ions (1.61 Å for CN ¼ XII)) [33]. By
using different methods, including neutron diffraction, [34,35]
Mossbauer€ spectroscopy [36e38], X-ray absorption (EXAFS) [39], and
3þ
electron-spin resonance [40], it has been found that the Sc shows a clear
preference for the R-block five-fold 2b and octahedral 4f 2 sites, while the
3þ
substitution of the Sc on the 12k sites is negligible. The reduction in M S
was ascribed to the reduced mag-netic exchange interactions between the
3þ 3þ
Fe ions diluted by the diamagnetic Sc , which result in a deviation from
the antiparallel spin arrangements [5,6,32].
The first possible explanation for the opposite influence of the Sc
substitution on the magnetic properties of the nanoplatelets compared to the
bulk might relate to the different site occupancies in the two different forms.
In this investigation we used a combi-nation of atomic-resolution high-angle
annular dark-field (HAADF) imaging and chemical analysis (energy-
dispersive x-ray spectros-copy (EDXS) and electron-energy loss spectroscopy
(EELS)) with a probe spherical-aberration (CS) corrected scanning-
transmission electron microscope (STEM) to determine the site of the Sc
incor-poration in the hexaferrite nanoplatelet structure. However, ab initio
calculations suggested that the increase in magnetic proper-ties with the Sc
substitution is actually directly related to specific two-dimensional magnetic
ordering due to the small thickness of the nanoplatelets.
2. Experimental
Two samples of hexaferrite nanoplatelets, unsubstituted BHF
nanoplatelets and Sc-substituted Sc-BHF nanoplatelets, were syn-thesized
using the hydrothermal method. A total of 200 mL of aqueous solution of
2þ 2þ 3þ 3þ 3
metal nitrates (20.8 mmol/L Ba , Ba / (Fe þSc ) ¼ 1/5, for Sc-BHF Fe
þ 3þ
/Sc ¼ 7, the used materials are listed in Supporting information) was
rapidly mixed into 200 mL of aqueous NaOH (4.65 mol/L) to co-precipitate
the corresponding hydroxides. The slurry was then sealed in an Inconel
pressure vessel (Parr Instrument Company) and heated at a rate of 3 C/min to
the final temperature, when the heating was switched-off. Because of the
relatively large thermal capacity, the temperature inside the autoclave started
3þ
to decrease after approximately 10 min. Since the addition of Sc effectively
suppresses the exaggerated growth during the hydrothermal synthesis of the
nanoplatelets [7,8], the two samples were synthesized at different
temperatures. The aim was to synthesize nanoplatelets of comparable size.
The unsubstituted BHF sample was synthesized at 160 C and the Sc-
substituted Sc-BHF sample at 250 C. The product was washed, first with
diluted nitric acid and, finally, with distilled water. Washing with nitric acid
dissolves any Ba-rich phases that may form due to the excess of Ba. Finally,
the product nanoplatelets were dried under vacuum at room temperature.
The morpho-structural characterization of the samples was carried out
3þ 200CF). XRD patterns were recorded with a PANalytical X' Pert PRO
diffractometer. The magnetic properties were measured with a vibrating-
sample magnetometer (VSM Lake Shore 7307) at room temperature and with
a SQUID (Quantum Design MPMS XL-
5) in the temperature range between 2 K and 350 K. Details of the
characterization methods are given in the Supporting information.
86 D. Makovec et al. / Acta Materialia 172 (2019) 84e91

Fig. 1. Different Fe lattice sites (trigonal 2b, tetrahedral 4f1, octahedral 12k, 2a, and 4f2) are marked on a schematic representation of the hexaferrite structure (a). Room-temperature magnetic
hystereses (b), TEM images (c, d) and corresponding width w D distributions (e, f) for BHF nanoplatelets (c, e) and Sc-substituted Sc-BHF nanoplatelets (d, f).

3. Results
3.1. Size, structure and magnetic properties of unsubstituted and Sc-
substituted Ba-hexaferrite nanoplatelets
The TEM (Fig. 1(c) and (d)) shows that the BHF nanoplatelets contained
two width populations of the nanoplatelets: apart from the well-crystalline,
~50-to-300-nm-wide hexagonal nano-platelets, also ultrafine, less-than-20-
nm-wide, discoid nano-platelets were present. The broad number-weighted
distribution of the BHF nanoplatelet widths (~60 ± 50 nm) shows that almost
40% of the nanoplatelets are smaller than 20 nm; however, they represent less
than 5% of the total volume (Fig. 1 (e)). The Sc-BHF nanoplatelets did not
contain the ultrafine discoid nanoplatelets and thus displayed a much narrower
width distribution of 53 ± 22 nm (Fig. 1 (f)).
The thickness of the nanoplatelets is, however, precisely defined by their
unique crystalline structure. Fig. 2 shows HAADF STEM images of the BHF
nanoplatelets oriented edge-on, with the basal surfaces parallel to the electron
beam. The images are characterized
by the rows of spots of various intensities representing the indi-vidual atomic
columns. Since the intensity of the spots in the “Z-contrast” HAADF images
depends on the column's average atomic number Z [41], the spots can be
directly related to the positions of the two cations of the barium hexaferrite:
2þ
the brightest spots represent the columns containing Ba ions, while the
3þ
spots of weaker intensity represent the columns containing the lighter Fe
2
ions (the O columns are too light to be visible in the HAADF images). The
projected structural model for the hexaferrite along the <1010> with marked
positions of the individual Fe lattice sites is superimposed over the
2 þ
experimental image in Fig. 2(c) to illus-trate the positions of the Ba and
3þ
Fe columns. The structure of the BHF nanoplatelet shown in Fig. 2(c)
contains only two rows of Ba columns. In the hexaferrite structure the row of
Ba columns marks the middle of a three-oxygen-layer hexagonal
2-
(BaFe6O11) R block, where the Ba columns alternate with the trigonal
Fe(2b) columns (Fig. 1(a)). The Ba/Fe(2b) row is sandwiched between two
rows of octahedral Fe(4f 2) columns. The row of Fe(12k) columns is at the
2þ
transition from the R block to a two-oxygen-layer cubic (Fe 6O8) S block.
The S block contains the three rows of Fe
 D. Makovec et al. / Acta Materialia 172 (2019) 84e91
Fig. 2. BF (a) and HAADF (b, c) STEM images of hexaferrite nanoplatelets oriented along the <1010> direction of their hexaferrite structure. In image (c) the projected hexaferrite structure is
2þ 3þ
superimposed to illustrate the positions of the Ba and Fe ions. Different Fe lattice sites (trigonal 2b, tetrahedral 4f1, octahedral 12k, 2a, and 4f2) are marked.
columns; a row of octahedral Fe(2a) columns is sandwiched be-tween two
rows of tetrahedral Fe(4f 1) columns. The inspection of a large number of
BHF nanoplatelets showed that their structure usually contains two R blocks
(Fig. 2(c)) or three R blocks (Fig. 2(a) and (b)), rarely four R blocks, but they
always terminated at the basal surfaces with the spinel S block. Note that the
image of the very surface of the nanoplatelets is somewhat affected by
various surface effects. In our previous studies [30,31] the epitaxial
maghemite layers were deposited on the basal surfaces of the nanoplatelets,
enabling undistorted images of their surface, i.e., coherent interfaces between
the hexaferrite core and the epitaxial layers. The imaging clearly showed that
the cationic sublattice of the hexaferrite nanoplatelets always terminates at the
basal sur-faces with the Fe(12k) plane, i.e., with the complete S block. The
thickness of the nanoplatelets varies in a step-wise manner with the number of
R blocks from 3.0 nm (for the two R blocks), over 4.1 nm (three R blocks), to
5.3 nm (four R blocks).
The structure of the Sc-BHF nanoplatelets also always termi-nated at the
basal surfaces with a complete S block. On average, the Sc-BHF nanoplatelets
were somewhat thinner than the BHF nano-platelets, as a vast majority
contained only two R blocks and only seldom did the Sc-BHF nanoplatelets
contain the three R blocks.
The distinct nanoplatelet structures also define their composi-tions. Due to
the surface termination with the S block they are al-ways enriched with Fe.
The theoretical compositions can be written with the formulas BaFe 15O23,
BaFe14O22, and BaFe13.5O21, for the two, three, and four R blocks,
respectively. The average composition of the Sc-BHF sample was
experimentally determined with an EDXS analysis of a large number of
Ba Fe Sc
individual nanoplatelets to be 1±0.08 14.9±0.12 0.87±0.10
Even though the Sc-substituted nanoplatelets, Sc-BHF, were smaller on
average than the unsubstituted BHF nanoplatelets, they displayed much better
room-temperature magnetic properties (Fig. 1(b)). The BHF nanoplatelets
2
displayed a MS of 16.1 Am /kg and a HC of 35.8 kA/m, while the Sc-BHF
2
showed a remarkably higher MS and HC of 38.1 Am /kg and 82.0 kA/m,
respectively. In part, the different magnetic properties of the two samples can
be ascribed to the different size distributions of the nanoplatelets. First, the
lower MS of the BHF nanoplatelets can be directly ascribed to the presence of
ultrafine, discoid nanoplatelets, which were not contained in the Sc-BHF
nanoplatelets. These ultrafine particles are super-paramagnetic with a very
2
weak MS below 2 Am /kg [26,31]. They could, therefore, decrease the overall
magnetization and change the shape of the hysteresis loop. A characteristic,
constricted, wasp-waisted-shape hysteresis loop is expected for the mixture of
the hard- and soft-magnetic materials [42,43]. However, the BHF sample
contained less than 5 vol% of these ultrafine super-paramagnetic nanoplatelets
(Fig. 2(e)), which do not noticeably influence the shape of the hysteresis loop
and cannot account for the large difference in the M S of the two
compositions. Moreover, the much broader size distribution of the larger
nanoplatelets in the BHF sample (excluding the superparamagnetic ultrafine
nanoplatelets) when compared to the Sc-BHF nanoplatelets might influence
the magnetization to some extent. S. Kirusu et al. [44] and M. Rosler€ et al.
[45] interpreted the dependence of MS on the size of the thicker barium-
hexaferrite nanoplatelets (~10 nm) in terms of a nonmagnetic surface layer.
They showed that the MS decreased with the increasing specific area of their
basal surfaces, while the effect of the side surfaces was negligible. The
thickness of the so-called effective nonmagnetic layer (d) was smaller for the
Co-Ti-
O.
x
88 D. Makovec et al. / Acta Materialia 172 (2019) 84e91

substituted hexaferrite (BaFe10.2Ti0.9Co0.9O19, d ¼ 0.7 nm) than for the

unsubstituted (d ¼ 1.3 nm). In contrast, our results [31] suggest that the
thickness has a dominant effect on the MS of our thinner nanoplatelets.
Because the growth is limited in the c-direction, the thickness of the
nanoplatelets remains almost constant with their widths. For example, a
majority of the BHF nanoplatelets contained three R structural blocks and
were 4.1 nm thick, while their widths varied from ~30 to 300 nm. At a
constant thickness, the specific area of the basal surfaces also remains
constant and the width distri-bution has no effect on the MS (if we consider
the influence of the nonmagnetic layer only on the basal surfaces, as in Refs.
[43,44]). Since the thickness of the nanoplatelets was considerably larger in
the unsubstituted sample than in the Sc-substituted sample, we can conclude
that the most important contribution to the increase in M S of the Sc-BHF
should be ascribed to the Sc incorporation into their structure.

The different magnetic properties of the two samples at room temperature

could be related to the changed temperature depen-dence of the magnetization
with the Sc incorporation. However, the two types of nanoplatelets showed
very similar temperature dependence and therefore the differences between
the magnetic properties of the two samples also remained large at 2K (see
Fig. SI1 in the Supporting information).

3.2. The site of the Sc incorporation into the hexaferrite

nanoplatelet structure
The extraordinary opposite effects of the Sc substitution in the
nanoplatelets compared to the bulk, i.e., the increase of M S in the
nanoplatelets and the decrease in the bulk [5,6,32] might be related to the
different lattice site occupation by the Sc. The substitution of diamagnetic
Sc
3þ
for the magnetic Fe
3þ
can have a large effect on the MS, depending on
3þ 2þ
the lattice site, while the Sc substitution for the diamagnetic Ba
3þ
would influence the MS to a much smaller extent. The Sc distribution over
the nanoplatelet struc-ture was analyzed using a combination of HAADF
imaging and EDXS/EELS mappings in a C S-corrected STEM. As the
analyses close to the surface of the free-standing nanoplatelets can be affected
by surface effects, the nanoplatelets were also analyzed after epitaxial
maghemite layers were deposited on their basal surfaces [30,31]. The
analyzes showed that the Sc is very inhomogeneously distributed in the as-
synthesized Sc-BHF nanoplatelets. In the HAADF images of the Sc-BHF
nanoplatelets oriented edge-on the intensity of the atomic columns of the R
blocks varied across many individual nanoplatelets. For example, the row of
mixed Ba and Fe(2b) columns on the left-hand side of the nanoplatelet's
HAADF image of Fig. 3 displays a much higher intensity than the Ba/Fe(2b)
row on the right-hand side. Moreover, the rows corresponding to the Fe(4f 2)
positions are well resolved in the left R block, whereas they are hardly visible
in the right R block. Measurements of the periodicity in the “uneven”
nanoplatelets' HAADF images showed that the R blocks are significantly
wider where they appear with a weaker intensity. In the case of the
nanoplatelet shown in Fig. 3 the brighter R block on the left was 6.7 Å wide
(the width of the block is measured as the distance between the two
consecutive Fe(12k) rows), while the weaker R block on the right was 7.3 Å
wide (theoretically, in the unsubstituted bulk barium hexaferrite the R block
and the S block are 6.6 Å and 5.1 Å wide, respectively). The width of the S
block remained constant at 5.1 Å across the nanoplatelets.
The elemental analyses unambiguously showed that the R blocks with the
larger width, which appeared on the HAADF images with the weaker
intensity of spots, are related to a higher con-centration of the incorporated
Sc. For example, Fig. 4 shows a HAADF STEM image of the hexaferrite
nanoplatelet with the
Fig. 3. HAADF STEM image of Sc-BHF nanoplatelet (HF) with epitaxial maghemite (M)
layers grown on both basal surfaces. Superimposed red curve shows intensity profile across the
image of the HF nanoplatelet. (For interpretation of the references to colour in this figure
legend, the reader is referred to the Web version of this article.)
corresponding EELS elemental maps. The nanoplatelet oriented along
<1010>HF contains three R blocks. The R block in the upper part of the image
is brighter and narrower than the two R blocks below. The EELS elemental
ions
maps clearly show an inhomogeneous distribution of the Sc: the Sc
concentration is low in the upper R block, but much higher in the lower two R
blocks. Moreover, it is evident that the Sc is preferentially concentrated in the
R blocks. Compared to the Ba signal originating from the individual Ba-
containing planes in the middle of the R blocks, the Sc signal shows a much
broader distribution, suggesting the Sc distribution over all three cation planes
of the R blocks. However, the lateral resolution of the elemental mappings is
too low to resolve between the Sc incorporation at the Ba and the Fe(2b) sites.
The inhomo-geneous Sc distribution across the nanoplatelets and the location
of the Sc preferentially in the R block were confirmed with a large number of
EELS and EDXS mappings (see also Figs. SI2 and SI3 in Supporting
information).
The large difference in the brightness of the spots corresponding to the Ba
columns in the neighboring R blocks with a varying Sc concentration on the
HAADF images can be explained by the sub-stitution of a part of the Ba with
the lighter Sc. In the extreme case, like the one presented in Fig. 3, the
intensity reduction of the Ba columns was up to 30% where the incorporation
2þ
of Sc was assumed. To estimate the percentage of the Ba substituted with
3þ
the Sc the experimental HAADF images were compared [46] with the
simulated images calculated using a multi-slice method and the frozen-
phonon approximation [47] for the structures at different thickness and with a
different degree of the Sc substitution (see Supporting information for
details). The analysis showed that the reduction in the Ba columns’ intensity
2þ 3þ
corresponds to 50e70% of Ba ions substituted with Sc ions, which seems
3þ 2þ
unrealistically high. Moreover, the substitution of the Sc for the Ba
$
(Sc Ba) would introduce extra charge into the structure. In principal, the
positive (donor) charge of the Sc substitution can be compensated either
electronically, by the reduction of Fe
3þ
to Fe
2þ $
(Sc Ba ¼ eʹ), or
 D. Makovec et al. / Acta Materialia 172 (2019) 84e91
Fig. 4. HAADF STEM image of Sc-BHF nanoplatelet (oriented along <1010>HF) with epitaxial spinel-ferrite layers grown on both basal surfaces with the corresponding EELS mappings.
Superimposed red curve shows intensity profile across the image of the HF nanoplatelet.
by the formation of ionized cation vacancies, (V Baʹʹ) or (VFeʹʹʹ). In the bulk
hexaferrites prepared by sintering at high temperature the extra donor charge
3þ
is preferentially compensated by the reduction of Fe at the 2b positions
[48,49]. The valence state of the Fe across the nanoplatelets was determined
using an analysis of the EELS spectra, as described in ref. 31. However, the
estimated average Fe valence was 3 þ and the variations across the
nanoplatelets were within the expected experimental uncertainty of the
method [31]. Much more realistic values for the substitution percentages,
20e30%, were obtained by assuming the compensation of the extra charge
3þ
with ionized barium vacancies, VBaʹʹ. As for the two incor-porated Sc
$
one Ba-vacancy is formed (2 Sc Ba ¼ VBaʹʹ), the incorporation has a very
large influence on the brightness of the Ba columns in the HAADF images.
The existence of charge-compensating Ba vacancies is consistent with the
large expansions of the R blocks observed where a higher concentration of the
Sc was incorporated. In the extreme cases, like the one presented in Fig. 3, the
R block with a higher concentration of the incorporated Sc can be even 0.6 Å
wider than the R block with a lower Sc concentration, whereas the widths of
the S blocks remained constant across the nanoplatelet. The local expansion
3þ
of the R block with the increased Sc incorporation is very large when
compared to the average expansion of the unit cell in the c-direction with the
Sc substitution in the bulk. In the bulk the c-lattice parameter is increased by
~0.2 Å for a comparable Sc con-centration [5,6,40]. (It should be noted that
the hexaferrite unit cell contains two R blocks.) The increased width of the R
block with the Sc incorporation can be partially ascribed to the substitution of
3þ 3þ
Fe ions (0.55 Å) at the 4f2 sites with the considerably larger Sc
3þ
(0.745 Å). The incorporation of the Sc at the 2b sites will influence the
expansion of the structure in the c-direction to a smaller extent, since the 2b
2þ 2
sites are situated in between the much larger Ba (1.61 Å) and O ions. The
3þ 2þ
substitution of the Sc for the Ba should have the opposite effect,
decreasing the R-block width. However, the formation of compensating Ba
vacancies accompa-nying the Ba substitution would considerably expand the
structure [50,51]. The cation vacancy can induce a local lattice expansion so
as to minimize the anion repulsions in the vicinity of the vacancy. The most
plausible explanation for the decreased intensity of the Ba columns in the R
blocks with increased Sc concentrations is therefore the substitution of a small
2þ 3þ
proportion of the Ba ions (20e30%) with Sc ions, with the simultaneous
formation of the ionized Ba vacancies for the charge compensation. Note that
neither the substitution of Ba
2þ 3þ
with Sc , nor the compensation of the donor
charge with VBaʹʹ has ever been reported for the hex-aferrites before. Most
3þ 2þ
probably, the Sc substitution for Ba and the formation of VBaʹʹ are only
possible in the thin, flexible
nanoplatelet structure, whereas such incorporations are not possible in the
bulk.
We attempted to homogenize the nanoplatelets’ composition using very
intensive stirring of the reaction suspension during the hydrothermal
synthesis; however, HAADF imaging still showed considerable
inhomogeneity of the Sc distribution. Remarkably, even when the Sc-BHF
nanoplatelets were subjected to 500 C the distribution of Sc over the platelet
remained very inhomogeneous (see Fig. SI10 in ESI). The nanoplatelets only
homogenized after annealing at 700 C for a very long time (several days).
ions
The inhomogeneity of the Sc distribution across the nano-platelets could
be a consequence of the specific development of their structure during the
hydrothermal synthesis. The hexaferrite nanoplatelets start to form already at
temperatures below 80 C. The initial nanoplatelets contain only one R block,
sandwiched between the two S blocks. With exaggerated growth at higher
temperature (above ~ 150 C) the nanoplatelets’ thicknesses in-crease
*
discretely with the addition of the RS segments to the initial SRS structure
[31]. If the Sc were to incorporate into the nano-platelets only during
exaggerated growth, the Sc would not be present in the R block originating
*
from the initial SRS structure (assuming negligible solid-state interdiffusion).
The EDXS analysis of the initial Sc-BHF nanoplatelets (hydrothermally
synthesized for 24 h at 80 C), however, showed incorporation of the Sc
*
already into the initial SRS -structured nanoplatelets, contradicting this
kinetic scenario. On the other hand, the segregation of the Sc at particular R
blocks can have a thermodynamic origin. As explained above, large local
distortions of the nanoplatelet structure accompany the incorporation of the
ions 3þ
Sc ions. These local distortions can be minimized by the inhomogeneous
distribution of Sc across the nanoplatelets.
3.3. Ab-initio calculations
The influence of the Sc substitution on the properties of the hexaferrite
nanoplatelets was simulated by calculating the total energy and the
magnetization within the framework of the density-functional theory [52e54].
In this manner we prepared 24 different cells with the Sc substituted at the
different Fe sites, which corre-spond to the composition BaFe 12-xScxO19 with
x ¼ 0.5. The con-structed model structures present one unit cell with a
* *
rearranged stacking sequence RSR S , which makes it possible to distinguish
between the in-block and the at-the-surface positions of the Sc atoms. An
example of a representative cell is shown in the Sup-plemental information
(Fig. SI11). All the considered structures were optimized by means of
calculating the equilibrium lattice parameters and relaxing the atomic
positions. Only a small
90 D. Makovec et al. / Acta Materialia 172 (2019) 84e91
variation of the theoretical lattice parameter was found for different positions
of the Sc atoms and in comparison with the nanoplatelet without the Sc.
However, already low concentrations of the Sc substitutions result in
relatively large changes in the magnetizations. The experimentally suggested
stresses in the nanoplatelet structures are therefore not responsible for the
observed changes in the magnetization. The calculated magneti-zations were
in the interval from 76% to þ76% of the value for the non-substituted platelet,
depending on the site of the substitution. However, none of the two models
with the most significant change in the magnetization corresponded to the
lowest total energy, hence to a stable structure. In both cases the Sc atom was
located in the S block. The highest magnetization was obtained if the Fe(12k)
atoms from the surface plane were substituted by a Sc atom, whereas such a
substitution at the Fe(2a) sites in the middle of the S block led to a large
decrease of the magnetization. In agreement with the experiment the most
stable structure was obtained in the case of the Sc substitution for the Fe of
the R block, in the vicinity of a Ba atom. In the case of the Sc incorporation at
the Fe(4f2) sites the calculated magnetization increased by 31% relative to the
non-substituted value. Although the agreement with experiment is not perfect,
it can be argued that a slightly higher concentration of Sc (which is difficult to
model) might yield a more pronounced enhancement of the magnetism. The
analysis of the calculated magnetization for other substitution sites hints that
the substitu-tion of magnetic Fe atoms by non-magnetic Sc atoms in
established magnetically ordered structures tends to destroy the magnetic
ordering as is the case in the bulk.
4. Discussion
3þ
It is well known that the incorporation of diamagnetic Sc ions into bulk
3þ
hexaferrites decreases their MS [5,6,34,40]. In contrast, the Sc substitution
clearly improved the magnetic properties of the nanoplatelets (Fig. 1(b)). A
3þ
similar effect on the magnetic properties was also observed when In was
3þ
substituted in the hexaferrite nanoplatelets [7]. The In has a similar ionic
3þ
radius (0.800 Å for CN¼VI) to the Sc (0.745 Å) and influences the
magnetic proper-ties of the bulk hexaferrite in a similar way [5,36,37]. The
3þ
effect of some other ions, e.g., Cr [7] and Co/Ti [45], was similar when
substituted in the nanoplatelets as in the bulk, i.e., they decreased the MS.
Even though the analysis of the Sc's incorporation into the nanoplatelet
structure showed some peculiarities, it gave no obvious answers to the
question as to why the Sc substitution has the opposite influence on the
magnetization of the nanoplatelets compared to the bulk. The preferential site
of Sc substitution for Fe in the nanoplatelets was found to be similar to that in
the bulk. The only clear difference in the Sc-site incorporation is the partial
3þ 2þ
substitution of the diamagnetic Sc for the diamagnetic Ba ; however, that
should not have a large influence on the MS. We can therefore assume that the
different magnetic structure appears as a result of super-exchange interactions
3þ
between the Fe ions at the five different lattice sites in the confined, two-
dimensional space of the nanoplatelet relative to that in the bulk.
In the bulk, the reduction in MS with the Sc substitution was ascribed to
the deviation from the antiparallel spin arrangements. The preferential
3þ
incorporation of the diamagnetic Sc at the 4f2 sites with the spin-down
configuration would theoretically in-crease the total magnetic moment when
3þ
assuming co-linear anti-parallel spin arrangements. However, the Sc
3þ
incorporation disturbs the super-exchange coupling with the Fe ions on the
12k sites, resulting in the deviation of the orientations of their magnetic
moments from the c-axis. The resulting configuration exhibits a magnetic
structure composed of helical blocks with different
angles between the adjacent blocks. Due to such reduced magnetic exchange
interactions significant spin canting starts to appear with the increasing degree
of the substitution, and helical spin config-urations further reduce the net
3þ
magnetization for larger Sc con-centrations. The evolution of the non-
collinear magnetic structure makes the c-axis no more preferential, which
results in a transition from the uniaxial to the planar magneto-crystalline
anisotropy, and consequently in a decrease of the magnetization [5,6,32]. This
mechanism seems not to be prevalent in the nanoplatelets. The ab-initio
calculations suggested that the opposite effect of the Sc substitution in the
nanoplatelets to that in the bulk can be ascribed to the two-dimensional
magnetic ordering in the platelets, prob-ably more pronounced in the S, Fe-
only blocks. It might be that the Sc atoms in the R blocks provide an indirect
magnetic interaction between the Fe atoms from the two adjacent S blocks,
which is reflected in a higher magnetization. The observed phenomenon, i.e.,
the opposite effect of the Sc substitution in the nanoplatelets than in the bulk,
clearly demonstrates the importance of the nanoscale behavior for the
magnetism.
5. Conclusions
3þ
The incorporation of Sc into the barium-hexaferrite structure has the
opposite effect on the saturation magnetization, M S, in the nanoplatelets than
in the bulk. In the nanoplatelets, approximately 50 nm wide and 3 nm thick,
the Sc-substitution improves the M S by more than twofold, whereas in the
bulk the substitution is seen to result in a decrease of the M S. A combination
of atomic-resolution imaging and elemental mappings in a scanning-
transmission electron microscope showed that this discrepancy between the
3þ
nanoplatelets and the bulk cannot be ascribed to the Sc substi-tution at
3þ 3þ 3þ
different Fe lattice sites. As in the bulk, the Sc ions substitute the Fe
ions preferentially at the 4f 2 and 2b lattice sites of the R blocks of the
* *
hexaferrite SRS R structure (S and R repre-sent a hexagonal (BaFe 6O11)
2-
2þ
and a cubic (Fe6O8) structural block, respectively). A clear difference
3þ
between the nano and the bulk was in the partial substitution of the Sc for
2þ
the Ba in the nanoplatelets, which was never reported for the bulk;
however, this cannot explain the large increase in the M S. The extra charge
2þ
introduced into the structure with the Ba substitution is compensated by the
formation of ionized Ba vacancies. On the basis of the results of the ab-initio
calculations, we conclude that the opposite effect of the Sc substitution on the
magnetic properties in the nanoplatelets than in the bulk can be ascribed to the
specific, two-dimensional magnetic ordering in the platelets.
Acknowledgments
The support of the Slovenia Research Agency within the Pro-gram P2-
0089 and the Project J2-8166 is gratefully acknowledged. We acknowledge
the CENN Nanocenter for the use of VSM equip-ment. We would also like to
thank Prof. Zvonko Jaglicic and Dr. Marko Jagodic for the SQUID
measurements.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.actamat.2019.04.050.
References
[1] R.H. Kodama, Magnetic nanoparticles, J. Mag. Mag. Mat. 200 (1) (1999) 359e372.
[2] X. Batlle, A. Labarta, Finite-size effect in fine particles: magnetic and transport
properties, J. Phys. D 35 (6) (2002) R15eR42.
[3] H.S. O'Neill, Temperature dependance of the cation distribution in zinc ferrite
 D. Makovec et al. / Acta Materialia 172 (2019) 84e91

(ZnFe2O4) from powder XRD structural refinements, Eur. J. Mineral. 4 (3) (1992)
571e580.
[27] M. Drofenik, I. Ban, D. Makovec, A. Znidarsic, Z. Jaglicic, D. Hanzel, D. Lisjak,
[4] D. Makovec, A. Kodre, I. Arcon, M. Drofenik, The structure of compositionally
The hydrothermal synthesis of super-paramagnetic barium hexaferrite par-
constrained zinc-ferrite spinel nanoparticles, J. Nanopart. Res. 13 (4) (2011) 1781e1790.
ticles, Mater. Chem. Phys. 127 (3) (2011) 415e419.
[5] S. Bierlich, F. Gellersen, A. Jacob, J. Topfer,€ Low-temperature sintering and magnetic [28] J. Wang, F. Zhao, W. Wu, G.O. Zhao, Finite-size scaling relation of the curie
properties of Sc- and In-substituted M-type hexagonal barium fer-rites for microwave applications, Mater. Res. temperature in barium hexaferrite platelets, J. Appl. Phys. 110 (12) (2011)
Bull. 86 (2) (2017) 19e23.
123909-1e123909-5.
[6] G. Albanese, A. Deriu, Magnetic properties of Al, Ga, Sc, in substituted barium ferrites: a
comparative analysis, Caramurgia Int. 5 (1) (1979) 3e10.
[7] D. Lisjak, M. Drofenik, Chemical substitution: an alternative strategy for controlling the
particle size of barium ferrite, Cryst. Growth Des. 12 (11) (2012) 5174e5179.

[8] D. Lisjak, M. Bukovec, K. Zupan, Suppression of the exaggerated growth of barium

3þ 3þ
ferrite nanoparticles from solution using a partial substitution of Sc for Fe , J. Nanopart. Res. 44 (2) (2016)
https://doi.org/10.1007/s11051-016-3348-7.

[9] R. Pullar, Hexagonal ferrites: a review of the synthesis, properties and appli-cations of
hexaferrite ceramics, Prog. Mat. Sci. 57 (7) (2012) 1191e1334.
[10] Y.I. Golovin, S.L. Gribanovsky, D.Y. Golovin, N.L. Klyachko, A.G. Majouga, A.M.
Master, M. Sokolsky, A.V. Kabanov, Towards nanomedicines of the future: remote magneto-mechanical
actuation of nanomedicines by alter-nating magnetic fields, J. Control. Release 219 (12) (2015) 43e60.
[11] C. Wu, Y. Shen, M. Chen, K. Wang, Y. Li, Y. Cheng, Recent advances in magnetic-
nanomaterial-based mechanotransduction for cell fate regulation, Adv. Mater. 30 (17) (2018) 1705673-
1e1705673-8.
[12] D.-H. Kim, P. Karavayev, E.A. Rozhkova, J. Pearson, V. Yefremenko, S.D. Bader,

V. Novosad, Mechanoresponsive system based on sub-micron chitosan-functionalized

ferromagnetic discs, J. Mater. Chem. 21 (2011) 8422e8426.
[13] D.-H. Kim, E.A. Rozhkova, I.V. Ulasov, S.D. Bader, T. Rajh, M.S. Lesniak,

V. Novosad, Biofunctionalized magnetic-vortex Microdiscs for targeted cancer-cell

destruction, Nat. Matter. 9 (2010) 165e171.
[14] D. Cheng, X. Li, G. Zhang, H. Shi, Morphological effect of oscillating magnetic
nanoparticles in killing tumor cells, Nanoscale Res. Lett. 9 (2014) 195-1e195-8.

[15] R. Mansell, T. Vemulkar, D.C.M.C. Petit, Y. Cheng, J. Murphy, M.S. Lesniak, R.P.
Cowburn, Magnetic particles with perpendicular anisotropy for me-chanical cancer cell destruction, Sci. Rep. 7
(2017) 4257-1e4257-7.
[16]
[17] A. Mertelj, D. Lisjak, M. Drofenik, M. Copic, Ferromagnetism in suspensions of
magnetic platelets in liquid crystal, Nature 504 (7479) (2013) 237e241.
[18]
[19] A. Mertelj, D. Lisjak, N. Osterman, M. Copic, Magneto-optic and converse
magnetoelectric effects in a ferromagnetic liquid crystal, Soft Matter 10 (45) (2014) 9065e9072.
[20] R. Sahoo, M.V. Rasna, D. Lisjak, A. Mertelj, S. Dhara, Magnetodielectric and
magnetoviscosity response of a ferromagnetic liquid crystal at low magnetic fields, Appl.
Phys. Lett. 106 (2015) 161905-1e161905-4.
[19] M. Shuai, A. Klittnick, Y. Shen, G.P. Smith, M.R. Tuchband, C. Zhu,

R.G. Petschek, A. Mertelj, D. Lisjak, M. Copic, J.E. Maclennan, M.A. Glaser, N.A.
Clark, Spontaneous liquid crystal and ferromagnetic ordering of colloidal magnetic
nanoplates, Nat. Commun. 7 (2016) 10394-1e10394-8.
[20] S.E. Kushnir, A.I. Gavrilov, P.E. Kazin, A.V. Grigorieva, Y.D. Tretyakova, M. Jansen,
Synthesis of colloidal solutions of SrFe12O19 plate-like nano-particles featuring extraordinary magnetic-field-
dependent optical trans-mission, J. Mater. Chem. 22 (2012) 18893e18901.
[21] A.A. Eliseev, A.A. Eliseev, L.A. Trusov, A.P. Chumakov, P. Boesecke, E.O. Anokhin,
A.V. Vasiliev, A.E. Sleptsova, E.A. Gorbachev, V.V. Korolev, P.E. Kazin, Rotational dynamics of colloidal
hexaferrite nanoplates, Appl. Phys. Lett. 113 (2018) 13106-1e13106-5.
[22] G. Ferk, P. Kranjc, A. Hamler, A. Mertelj, F. Cebollada, M. Drofenik, D. Lisjak,
Monolithic magneto-optical nanocomposites of barium hexaferrite platelets in PMMA, Sci. Rep. 5 (2015)
11395-1e11394-8.
[23] D. Lisjak, S. Ovtar, The alignment of barium ferrite nanoparticles from their suspensions
in electric and magnetic fields, J. Phys. Chem. B 117 (6) (2013) 1644e1650.

[24] S. Ovtar, D. Lisjak, M. Drofenik, Preparation of oriented barium hexaferrite films by

electrophoretic deposition, J. Am. Ceram. Soc. 94 (10) (2011) 3373e3379.

[25] M. Drofenik, I. Ban, G. Ferk, D. Makovec, A. Znidarsic, Z. Jaglicic, D. Lisjak, The

concept of a low-temperature synthesis for superparamagnetic BaFe12O19 particles, J. Am. Ceram. Soc. 93 (6) (2010)
1602e1607.
[26] D. Primc, D. Makovec, D. Lisjak, M. Drofenik, Hydrothermal synthesis of ul-trafine
barium hexaferrite nanoparticles and the preparation of their stable suspensions, Nanotechnology 20 (31) (2009)
315605-1e315605-9.
[29] S.E. Kushnir, A.I. Gavrilov, P.E. Kazin, A.V. Grigorieva, Y.D. Tretyakova, hexaferrites, Phys. Rev. B 92 (2015) 125125-1e125125-10.
[50] U. Aschauer, R. Pfenninger, S.M. Selbach, T. Grande, N.A. Spaldin, Strain
M. Jansen, Synthesis of colloidal solutions of SrFe 12O19 plate-like nano-particles featuring extraordinary
magnetic-field-dependent optical trans-mission, J. Mater. Chem. 22 (36) (2012) 18893e18901. controlled oxygen vacancy formation and ordering in CaMnO3, Phys. Rev. B 88
[30] B. Belec, G. Drazic, S. Gyergyek, B. Podmiljsak, T. Gorsak, M. Komelj, J. Nogues, (2013) 054111-1e054111-7.

D. Makovec, Novel Ba-hexaferrite structural variations stabilized on the nanoscale as building blocks for
epitaxial bi-magnetic hard/soft sandwiched maghemite/hexaferrite/maghemite nanoplatelets with out-of-plane
easy axis and enhanced magnetization, Nanoscale 9 (2017) 17551e17560.
[31] D. Makovec, B. Belec, T. Gorsak, D. Lisjak, M. Komelj, G. Drazic, S. Gyergyek, Discrete
evolution of the crystal structure during the growth of Ba-hexaferrite nanoplatelets, Nanoscale (2018),
https://doi.org/10.1039/C8NR03815E.
[51] H. Kim, J.Y. Zhang, S. Raghavan, S. Stemmer, Direct observation of Sr vacancies
in SrTiO3 by quantitative scanning transmission electron microscopy, Phys.
Rev. X 92 (2016) 041063-1e041063-7.
[52] P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli,
G.L. Chiarottia, M. Cococcioni, I. Dabo, A.D. Corso, S. Fabris, G. Fratesi, S. de

[32] Y. Tokunaga, Y. Kaneko, D. Okuyama, S. Ishiwata, T. Arima, S. Wakimoto, Gironcoli, R. Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj, M. Lazzeri,
L. Martin-Samos, N. Marzari, F. Mauri, R. Mazzarello, S. Paolini, A. Pasquarello,
K. Kakurai, Y. Taguchi, Y. Tokura, Multiferroic M-type hexaferrites with a room-temperature conical
state and magnetically controllable spin helicity, Phys. Rev. Lett. 105 (2010) 257201-1e257201-4. L. Paulatto, C. Sbraccia, S. Scandolo, G. Sclauzero, A.P. Seitsonena,
A. Smogunov, P. Umari, R.M. Wentzcovitch, Quantum espresso: a modular and open-
[33] R.D. Shannon, Revised effective ionic radii and systematic studies of inter-atomic distances in source software project for quantum simulations of materials, J. Phys. Condens. Matter 21
halides and halcogenides, Acta. Cryst. A32 (5) (1976) 751e767. (39) (2009) 395502-1e395502-19.
[53] N. Troullier, J.L. Martins, Efficient pseudopotentials for plane-wave calcula-tions,
[34] O.P. Aleshko-Ozhevskii, V.A. Lyubimtsev, M.I. Namtalishvili, I.I. Yamzin, Angled block Phys. Rev. Lett. 43 (1991) 1993e2006.
magnetic structure in hexagonal ferrite, Sov. Phys. Crys. 16 (1972) 711e712.
[54] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made
simple, Phys. Rew. Lett. 77 (1996) 3865e3868.
[35] M.I. Namtalishvili, O.P. Aleshko-Ozhevskii, I.I. Yamzin, Spin ordering in BaFe 12-X O19 (M) hexagonal ferrites, Sov. Phys. Solid
State 13 (1972) 2137e2138.
[36] G. Albanese, A. Deriu, E. Lucchini, G. Slokar, Mossbauer€ investigation of in and Sc substituted
barium hexaferrite, Appl. Phys. A 26 (1) (1981) 45e50.
57 57
[37] T.M. Clark, B.J. Evans, G.K. Thompson, S. Freeman, Fe Fe Mossbauer€ spec-troscopic
investigation of complex magnetic structures in Ga, Sc, and in substituted M-type hexagonal ferrites, J. Appl.
Phys. 85 (8) (1999) 5229e5230.
[38] A.S. Kamzin, V.L. Rozenbaum, L.P. Ol’khovik, Mossbauer€ studies of the surface and bulk
magnetic structure of Scandium-substituted Ba-M-type hexaferrites, Phys. Solid State 41 (3) (1999) 433e439.
[39] A. Yang, Y. Chen, Z. Chen, C. Vittoria, V.G. Harris, Magnetic and atomic structure parameters of
Sc-doped barium hexagonal ferrites, J. Appl. Phys. 103 (2008) 07E511-1e07E511-3.
[40] R. Díaz-Pardo, S. Bierlich, J. Topfer,€ R. Valenzuela Monjaras, Electron spin resonance (ESR) of
magnetic sublattices in Sc-substituted barium hexaferrite, AIP Adv. 6 (5) (2016) 055202-1e055202-5.
[41] S.J. Pennycook, P.D. Nellist, Scanning Electron Microscopy, Springer, New York, 2011.

[42] P.J. Wasilewsk, Magnetic hysteresis in natural materials, Earth Planet. Sci. Lett. 20 (1973) 67e72.

[43] D. Primc, D. Makovec, Composite nanoplatelets combining soft-magnetic iron oxide with hard-
magnetic barium hexaferrite, Nanoscale 7 (2015), 2688-2679.

[44] S. Kurisu, T. Ido, H. Yokoyama, Surface effect on saturation magnetization of Co and Ti

substituted Ba-ferrite fine particles, IEEE Trans. Magn. Mag- 23 (1987) 3137e3139.

[45] M. Rosler,€ P. Gornert,€ E. Sinn, Structural and magnetic properties of Ba-ferrite fine particles
grown by glass crystallization, Z. Physik D Atoms, Mol. Clust. 19 (1991) 279e281.
[46] J.M. Le Beau, S. Stemmer, Experimental quantification of annular dark-field images in scanning
transmission electron microscopy, Ultramicroscopy 108 (12) (2008) 1653e1658.

[47] K. Koch, Determination of Core Structure Periodicity and Point Defect Density along
Dislocations, Arizona State University, 2002.
[48] A.M. Van Diepen, F.K. Lotgering, Mossbauer€ effect in LaFe12O19, J. Phys. Chem.
Solids 35 (12) (1974) 1641e1643.

[49] V. Chlan, K. Kouril, K. Ulicna, H. Stepankova, J. Topfer€ D. Seifert, Charge

localization and magnetocrystalline anisotropy in La, Pr, and Nd substituted Sr