Applied Physics A (2021) 127:488

https://doi.org/10.1007/s00339-021-04620-8

Polybenzoxazine/Mg–Zn nano‑ferrite composites: preparation,

identification, and magnetic properties
Marwa M. Hussein1 · Samia A. Saafan1 · N. A. Salahuddin2 · Maha K. Omar1

Received: 10 April 2021 / Accepted: 23 May 2021 / Published online: 4 June 2021
© The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature 2021

Abstract
In the present work, nano-ferrites of chemical composition: M ­ gxZn1−xFe2O4 where x = 0.0, 0.3, 0.7, and (1) have been
prepared by using two chemical methods to obtain the pure desired compositions without undesired phases. Benzoxazine
monomer (BZ) has been synthesized using aniline, paraformaldehyde, and phenol through Mannich condensation reaction
followed by thermal curing to produce a pristine polymer. Specified weights of ferrites have been mixed with the monomer
followed by thermal treatment to obtain the composites. The X-ray diffraction (XRD) and Fourier transform infrared (FTIR)
analysis have been used to ensure the formation of the desired ferrites, BZ, polybenzoxazine (PBZ), and/or composites. The
XRD has been used also to determine some of the structural properties of the prepared ferrites. Furthermore, the average
particle size of the ferrite samples has been calculated from the XRD patterns and it has ranged from 17.2 to 31.5 nm which
is in fair agreement with the calculated average particle size from the transmission electron microscope (TEM) images. For
investigating the magnetic properties of the samples, the vibrating sample magnetometer (VSM) has been used at room tem-
perature. The saturation magnetization ­(Ms) has increased significantly in the Mg ferrite samples and their composites with
PBZ by increasing the zinc content. Also, ­Ms has decreased with increasing the PBZ ratio in the composites. The coercivity
­(Hc) has decreased by increasing zinc content in all samples, while increased in the composite samples with higher amounts
of PBZ. The composites under investigation may be used in interesting device applications and coatings.

Keywords Ferrites · Benzoxazine · Polybenzoxazine · Composites · Structural properties · Magnetic properties

1 Introduction and the concentration of reactants or doped impurities [3].

Ferrites have been among the most studied materials for dec-
ades, having a very good advantage of the ability to exist in
solid bulk form, thin layers, and nanoparticles, giving them
the possibility to be used in too many diverse fields [1].
Ferrites with different crystal structures are widely used in
daily life applications, from which the spinel structure is the
most important one because of the useful combination of
high dielectric property, ferrimagnetic behavior, and ease of
preparation [2]. Attempts to control the magnetic and elec-
trical properties of ferrites have been explored by changing
some conditions of preparation such as sintering temperature
* Marwa M. Hussein
marwa.mostafa1@yahoo.com
1
Physics Department, Faculty of Science, Tanta University,
Tanta 31527, Egypt
2
Chemistry department, Faculty of Science, Tanta University,
Tanta 31527, Egypt
Nowadays, producing lightweighted, tunable, and multi-
functional materials is an avoidable task for researchers.
Nanoparticle spinel ferrites have been very attractive for
this reason. Those magnetic nanoparticles represent a class
of nanoparticles which is needed in biomedical applications
such as magnetic resonance imaging, drug transport, guiding
carriers, and harmless heating for killing cancer cells [4].
Other applications are also covering a wide range of various
fields such as permanent magnet production, spintronics,
magnetic refrigeration, attenuators, magnetic data storage,
gas sensors, photocatalysis, antennas, telecommunication
cores in inductors, electromagnets, and transformers. Also,
it is well known that radar-absorbing paint may contain fer-
rite nanoparticles [5, 6]. Mg–Zn ferrite in particular is very
interesting because of its low cost of preparation along with
the low level of losses at high frequencies. [7]. At the same
time, making composites of this nanoparticle ferrite with
a polymer may serve in opening new fields of applications
through the protection of being broken as the ferrites are

13
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488 Page 2 of 11 M. M. Hussein et al.

known to be brittle [8]. Among these potential applications 2 Experimental details

is the manufacture of microwave absorbing materials having
actually two components of absorption: magnetic and dielec-
tric absorbing components; where their roles are absorbing
magnetic and electric components of the incident electro-
magnetic waves, respectively [9].
PBZs are a versatile group of phenolic polymers that have
excellent flame retardant, heat resistance, low dielectric
properties, low surface energy, superior membrane proper-
ties at high temperature, low shrinkage, a high char yield, no
strong acid catalysts are required for curing, no by-products
are released during curing, cheap, and low water absorption
[11, 12, 21].
The fact that nano-ferrites can be embedded in polymers
may open the doors for other applications. Embedding nano-
ferrites into PBZ may enhance the sample properties includ-
ing lightweight, durability, and/or improved AC properties
[10, 12].
2.1 Preparation of nano‑ferrites
MgxZn1−xFe2O4 nanoparticles (where x = 0.3, 0.7, and 1)
have been synthesized by the citrate precursor technique
(citrate–nitrate auto-combustion method) as follows:
Grained powders of Mg(NO3)2.6H2O, Zn(NO3)2.6H2O,
Fe(NO3)3.9H2O, and ­C6H8O7 have been weighed in proper
ratios, as shown in Table 1, such that the proportions of
anhydrous citric acid to trivalent metal ions to divalent metal
ions used have been 3:2:1 [13, 14]. Aqueous solutions of
these nitrates have been made by using distilled water then
stirring for 20 min without heating to increase the homoge-
neity of the mixture before adding the citric acid. Finally,
ammonium hydroxide has been added drop-wise to the mix-
ture until the pH has been raised to approximately 8.0 [15,
16]. The mixture has been heated to about 100 °C for 2 h. A

Table 1  The purity, brand, and quantity (g and/or ml) of chemicals/solvents used to synthesis the ­MgxZn1−xFe2O4 nanoparticles (where x = 0.0,
0.3, 0.7, and 1), BZ monomer, and PBZ
Sample Chemicals/solvents Purity Brand Quantity (g and/or ml) Distilled
water
(ml)

Citrate precursor technique

MgFe2O4 Mg(NO3)2.6H2O 98% Loba Chemie 22.2 g in ➝ 30 ml
Fe(NO3)3.9H2O 98% 70 g in ➝ 50 ml
C6H8O7 99.5% 49.1 g in ➝ 50 ml
NH4OH (solution) Concentration 30% 400 ml
Mg0.7Zn0.3Fe2O4 Mg(NO3)2.6H2O 98% 14.5 g in ➝ 30 ml
Zn(NO3)2.6H2O 98% 7.2 g in ➝ 30 ml
Fe(NO3)3.9H2O 98% 66 g in ➝ 50 ml
C6H8O7 99.5% 46.3 g in ➝ 50 ml
NH4OH (solution) Concentration 30% 400 ml
Mg0.3Zn0.7Fe2O4 Mg(NO3)2.6H2O 98% 5.7 g in ➝ 30 ml
Zn(NO3)2.6H2O 98% 15.7 g in ➝ 30 ml
Fe(NO3)3.9H2O 98% 61.2 g in ➝ 50 ml
C6H8O7 99.5% 43 g in ➝ 50 ml
NH4OH (solution) Concentration 30% 400 ml
Co-precipitation technique
ZnFe2O4 ZnCl2 98% Loba Chemie 9.8 g in ➝ 150 ml
FeCl3 98% 23.3 g in ➝ 150 ml
NaOH 98% 23.5 g in ➝ 150 ml
BZ monomer
BZ Phenol 99.5% LANXESS 64 g
Paraformaldehyde 99% 38.4 g
Aniline 99% 60.8 ml
PBZ
PBZ THF 99% LANXESS
CHCl3 99.8% Loba Chemie

13
Polybenzoxazine/Mg–Zn nano‑ferrite composites: preparation, identification, and magnetic…
formed viscous gel has been self-ignited to give eventually
a fine and brown powder of the ferrite.
The ­ZnFe2O4 sample has been prepared by the chemi-
cal co-precipitation technique because it is one of the most
excellent methods for the formation of nanoparticles, less
expensive, and easier to be performed [17] following the
reported method in [18, 19]. First, aqueous solutions of
­ZnCl2 and ­FeCl3 have been mixed with Zn/Fe ion ratio of
1:2 [18, 19] (shown in Table 1 too) and stirred for 15 min
at room temperature. Then, the pH has been adjusted to 12
by adding NaOH solution drop-wise [20]. Finally, the solu-
tion has been heated to 90 °C with magnetic stirring for 2 h
till nano-ferrites have been formed in the form of a brown
precipitate. The precipitate has been cooled and washed
with distilled water four times to remove NaCl residuals.
The removal of NaCl has been confirmed by a lead acetate
test. The precipitated zinc ferrite has been dried and sintered
at 1000 °C for 6 h.
2.2 Preparation of BZ monomer
BZ has been synthesized by the solvent-less one-pot Man-
nich condensation method. Phenol, paraformaldehyde, and
aniline with molar ratios 1:2:1 have been stirred for 2 h in
an oil bath at 90 °C. Scheme (1) explains the formation of
the BZ monomer [21, 22].
The final product has been dissolved in C
­ HCl3 and then
washed with NaOH solution to remove any residuals of
sodium chloride then dried at 50 °C.
2.2.1 Preparation of PBZ and PBZ/ MgxZn1−XFe2O4
composites
At first, four grams of BZ have been placed in a glass dish
treated with dimethyldichlorosilane. The sample has been
cured thermally following a particular curing cycle starting
at 100 °C and ending at 230 °C for 5.5 h. Scheme 2 shows
the ring-opening polymerization of the monomer.
For preparing the PBZ–nanoferrite composites with the
desired ratios, we have used [70%ferrite (1.4 g): 30%BZ
(0.6 g) and 30%ferrite (0.6 g): 70%BZ (1.4 g)]. The BZ
monomer has been dissolved in 25 ml of tetrahydrofuran
Scheme 1  One-pot Mannich
condensation synthesis of
benzoxazine
Page 3 of 11 488
Scheme 2  Ring-opening polymerization of benzoxazine
(THF) and the ferrite has been separately dispersed in 25 ml
of (THF). Then, they have been mixed together and ultra-
sonicated for 20 min. The mixture has been heated to 70 oC
with stirring for 24 h. The samples have been cured ther-
mally following the curing cycle mentioned above [12].
2.3 Characterization
The BZ and PBZ have been characterized by FTIR spectros-
copy (Bruker Tensor 27) in the Central laboratory of Tanta
University in the range of 400–4000 ­cm−1. The prepared
ferrites, PBZ, and composites have been characterized by
using XRD (APD 2000 PRO) in the Central laboratory of
Tanta University using (Cu-Kα radiation with λ = 1.54 Å).
The average particle size of the ferrite samples has been
determined by using (TEM) (JEM-2100) at The National
Research Center in Cairo. The magnetic properties of fer-
rites and composites have been investigated by the VSM
using the model (Lake Shore 7410) at the National Research
Center in Cairo. The applied magnetic field has been varied
within ± 20 kOe at room temperature.
2.4 Results and discussion
2.4.1 XRD analysis
Figures 1, 2, 3, and 4 show the XRD plots of the prepared
ferrites ­MgxZn1−xFe2O4; where (x = 0.0, 0.3, 0.7, and 1)
clarifying the computerized matching which confirms
the formation of the required ferrites only without any
impurities. Figures 5, 6, 7, and 8 show the XRD plots
of the ferrites along with their composites to facilitate
13
488 Page 4 of 11 M. M. Hussein et al.

Fig. 1  X-ray diffraction patterns of the as-prepared ­MgFe2O4 with Fig. 3  X-ray diffraction (XRD) patterns of the as-prepared
computerized matching ­Mg0.3Zn0.7Fe2O4 with the computerized matching

Fig. 2  X-ray diffraction patterns of the prepared Z

­ nFe2O4 with com- Fig. 4  X-ray diffraction patterns of the as-prepared ­Mg0.7Zn0.3Fe2O4
puterized matching with computerized matching

the comparison. It is obviously revealed that all of the 12

samples have a single-phase cubic spinel crystal structure
with no impurity peaks. The presence of the characteristic
peaks presenting the (220), (311), (400), (422), (511), and
(440) planes is obviously detected in agreement with the
literature [23]. It is worth mentioning here that the pure
Zn ferrite sample has been prepared by the co-precipita-
tion method, whereas the other ferrite samples have been
prepared by the citrate precursor method, as mentioned
above. It is noticed that the peaks of ferrites have been
also recognized in the composites. It is worth mentioning
that by inserting the ferrite in the PBZ, the main char-
acteristic peaks of the ferrites have been slightly shifted
Fig. 5  X-ray diffraction (XRD) patterns of a ­MgFe2O4, b ­MgFe2O4/
and broadened, most probably indicating the formation of PBZ 30%, M ­ gFe2O4/PBZ 70%

13
Polybenzoxazine/Mg–Zn nano‑ferrite composites: preparation, identification, and magnetic… Page 5 of 11 488

some hydrogen bonding between the phenolic OH in PBZ

and some of the oxygen atoms involved partially in cova-
lent bonding in the (mainly ionic compound) of ferrites.
This may be considered as evidence that those ferrites are
not completely ionic compounds. The crystalline size has
been calculated using Scherrer’s formula:
k𝜆
R= ;
𝛽1∕2 cos 𝜃

where 𝛽1∕2 is the full width at half maximum (FWHM)

Fig. 6  X-ray diffraction (XRD) patterns of a ­ZnFe2O4, b ­ZnFe2O4/
PBZ 30%, (c) ­ZnFe2O4/PBZ 70%
of the main peak representing the planes (311), 𝜃 is the
Bragg’s angle, k is the constant dependent of crystallite
shape (= 0.89 for cubic crystal), and 𝜆 is the X-ray wave-
length (= 1.54 Å).
Lattice constant has been calculated by the following
relation:
√
a = d h2 + k 2 + l 2 ;

where d is the interplanar spacing given by the following

eq. (Bragg’s eq.):
n𝜆
d=
2 sin 𝜃
X-ray density (­ Dx) of all samples has been calculated too
by using:
8M
Dx = ;
NA a3

where M is the molecular weight of the sample, NA is

Avogadro’s number, and ­a3 is the unit cell volume. The
measured density ­(Dm) of the samples which have been
Fig. 7  X-ray diffraction (XRD) patterns of a ­Mg0.3Zn0.7Fe2O4, b
­Mg0.3Zn0.7Fe2O4/PBZ 30%, c ­Mg0.3Zn0.7Fe2O4/PBZ 70% pressed into disks has also been determined by:
m
Dm = ;
Vol
where m is the mass of the sample and Vol is the volume
of the sample. Finally, the porosity (P) has been calculated
by [3, 4]:
Dm
P=1−
Dx

The magnetic ions’ distance (jump length) in the tetrahe-

dral A-site ­LA−A (Å), octahedral B-site ­LB−B (Å), and shared
sites ­LA−B (Å) has been calculated using the relations [24]:
√ √ √
3 2 11
LA−A = a , LB−B = a , and LA−B = a
4 4 8
All of these results are listed in Table 2. The crystalline
Fig. 8  X-ray diffraction (XRD) patterns of a ­Mg0.7Zn0.3Fe2O4, (b) size has ranged from 17.2 to 31.5 nm as shown in Table 2.
­Mg0.7Zn0.3Fe2O4/PBZ 30%, c ­Mg0.7Zn0.3Fe2O4/PBZ 70% In the samples, prepared with auto-combustion method,

13
488 Page 6 of 11 M. M. Hussein et al.

Table 2  The Lattice constant a (Å), crystallite size R (nm), measured density D (kg/m3), X-ray density ­Dx (kg/m3), porosity P, ­LA−A (Å), ­LB−B (Å), ­LA−B (Å), average particle size from (TEM)

R(nm) Average parti-

cle size from (TEM)

23.9
21.7
16.8
27.9
LA−B (Å)

3.486
3.488
3.499
3.494
LB−B (Å)

2.973
2.974
2.984
2.980
LA−A (Å)

Fig. 9  X-ray diffraction (XRD) pattern of polybenzoxazin

3.641
3.643
3.655
3.650
0.543
0.530
0.553
0.408
P
Dx (kg/m3)

4466.2
4734.9
5031.3
5345.4
D (kg/m3)

2039.3
2223.6
2246.0
3162.0
eter (standard deviation) (Å) particle size from
Error bar for lattice param- R(nm) average

XRD

22.9
20.2
17.2
31.5

Fig. 10  a, b, c TEM micrograph of M­ gFe2O4 nanoparticles, d Image

of ­MgFe2O4 in the diffraction mode
(nm), and error bar (Å) for lattice parameter of ferrite samples

the crystalline size (R) has been found to decrease with

0.014
0.007
0.041
0.032

increasing Zn content. The observed increase in the lattice

parameter (a) with increasing the Zn content in the mixed
A (Å)

8.410
8.414
8.442
8.430

ferrite samples may be attributed to the smaller M­ g2+ ionic

2+
radius than the ­Zn ionic radius, in agreement with the
literature [25, 26]. It is noticed that the two used prepara-
Mg0.7Zn0.3Fe2O4 (Citrate precursor method)
Mg0.3Zn0.7Fe2O4 (Citrate precursor method)
Sample and method of preparation

tion methods have led to the formation of fine particles

in the nanometer range. The theoretical density ­Dx of the
MgFe2O4 (Citrate precursor method)

ZnFe2O4 (Co−precipitation method)

samples has generally increased with increase in the Zn

content, and it can be attributed to the greater molecular
weight of Zn ion than that of Mg ion [27]. This increase is
more effective and predominates over the small rise of the
lattice parameter where the porosity has slightly increased
[28]. The theoretical density has been found to have a
reverse trend compared to that of the porosity as expected,

13
Polybenzoxazine/Mg–Zn nano‑ferrite composites: preparation, identification, and magnetic…
Fig. 11  a, b, c TEM micrograph of ­ZnFe2O4 nanoparticles, d Image
of ­ZnFe2O4 in the diffraction mode
Fig. 12  a, b, c TEM micrograph of M ­ g0.3Zn0.7Fe2O4 nanoparticles, d
Image of ­Mg0.3Zn0.7Fe2O4 in the diffraction mode
except for the sample of x = 0.3 which has opposed the
trend, this is most probably due to adding more PVA as
a binder to this sample while preparing the pellets. The
changes in L­ A−A, ­LB−B, and L
­ A−B have followed the slight
increase in the lattice parameters as expected from their
equations.
In Fig. 9, pure PBZ has exhibited a broad peak centered
at 2θ ≈ 19º and expanded approximately from 15.55° to
31.5° indicating its amorphous nature [29, 30].
Page 7 of 11 488
Fig. 13  a, b, c TEM micrograph of M ­ g0.7Zn0.3Fe2O4 nanoparticles, d
Image of ­Mg0.7Zn0.3Fe2O4 in the diffraction mode
Fig. 14  FTIR spectra of a Benzoxazine monomer, b Polybenzoxazine
2.5 TEM
Figures 10, 11, 12, and 13 show TEM images taken for the
ferrite samples ­MgxZn1−xFe2O4; where (x = 0.0, 0.3, 0.7, and
1), from which the average of the particle size has been cal-
culated and it has ranged from 16.8 to 27.9 nm which is in
fair agreement with the value calculated from the X-ray data.
All the high-resolution transmission electron microscope
micrographs for the Mg ferrite and the Zn ferrite show some
fine particles and a few agglomerations. The diffraction pat-
terns taken by the microscope in the diffraction mode show
ring patterns that confirm the polycrystalline spinel structure
but it is obvious that the SAED of ­ZnFe2O4 shows more
crystallinity than that of ­MgFe2O4. The particle size has
been found to increase with increasing Mg, which may be
evidence that increasing magnetic ions has contributed—in
13
488 Page 8 of 11
Fig. 15  Magnetic hysteresis loops of a ­MgFe2O4, b ­MgFe2O4/PBZ
30%, c ­MgFe2O4/PBZ 70%
Fig. 16  Magnetic hysteresis loops of a ­ZnFe2O4, b ­ZnFe2O4/PBZ
30%, c ­ZnFe2O4/PBZ 70%
addition to other factors—to the increase in agglomeration
and hence increasing the particle size.
2.6 FTIR of BZ and PBZ
The FTIR spectra of the BZ monomer and the PBZ are
compared in Fig. 14. In the case of BZ monomer, a peak
at ~ 752 ­cm−1 has occurred which is assigned to ortho-disub-
stituted benzene and a peak at ~ 943 ­cm−1 which is due to the
stretching of C-O in epoxide group [31]. The peak observed
at 1500 is attributed to the tri-substituted benzene ring mode
in the oxazine ring structure, whereas the peaks observed
at 1230 and 1030 ­cm−1 may be attributed to C–O–C asym-
metric and symmetric stretching modes, respectively [29].
In polybenzoxazine, the disappearance of the peaks at
1230 ­cm−1 (C–O–C) and 943 ­cm−1 (oxazine) ensures the
ring-opening polymerization of BZ [29, 30]. The absorp-
tion peak at 1570 ­cm−1 may correspond to the stretching
vibration of the C = N. The new absorption peak appearing
13
M. M. Hussein et al.
Fig. 17  Magnetic hysteresis loops of a ­Mg0.3Zn0.7Fe2O4, b
­Mg0.3Zn0.7Fe2O4/PBZ 30%, c ­Mg0.3Zn0.7Fe2O4/PBZ 70%
Fig. 18  Magnetic hysteresis loops of a ­Mg0.7Zn0.3Fe2O4, b
­Mg0.7Zn0.3Fe2O4/PBZ 30%, c ­Mg0.7Zn0.3Fe2O4/PBZ 70%
at 1425 ­cm−1 is most probably attributed to the tetra-sub-
stituted benzene ring, confirming the ring-opening polym-
erization of the BZ. The intense absorption band at about
3460 ­cm−1 indicates the asymmetric stretching OH in both
polybenzoxazine and benzoxazine samples [30, 32].
2.7 VSM magnetic measurements
Some magnetic properties have been measured by using
a vibrating sample magnetometer (VSM) at room tem-
perature for all ferrite and composite samples as shown
in Figs. 15, 16, 17, 18 and in Table 3. The figures display
the hysteresis loops, from which the remanent magnetiza-
tion ­(Mr), the saturation magnetization (­ Ms), the coercivity
­(Hc), and the total area of the loops have been extracted.
All of the hysteresis loops are narrow with a relatively
small total area (shown in the last column of Table 3) and
small coercive magnetic fields H ­ c. This is categorizing
Polybenzoxazine/Mg–Zn nano‑ferrite composites: preparation, identification, and magnetic… Page 9 of 11 488

Table 3  Values of ­Ms, ­Mr, ­Hc, Sample Ms (emu/g) Mr (emu/g) Hc (G) Squareness Area-total (erg/g)
squareness, and total-area of ­(Mr/Ms)
samples
MgFe2O4 25.55 7.454 106.65 0.291 7925.6
ZnFe2O4 4.37 0.555 40.82 0.127 950.53
Mg0.7Zn0.3Fe2O4 44.43 8.200 64.94 0.184 9966.2
Mg0.3Zn0.7Fe2O4 40.58 5.361 50.39 0.132 4691.6
MgFe2O4/PBZ 30% 21.49 5.904 112.24 0.274 7449.3
ZnFe2O4/PBZ 30% 3.28 0.125 12.65 0.0381 508.69
Mg0.7Zn0.3Fe2O4/PBZ 30% 33.87 4.963 68.95 0.146 6447.5
Mg0.3Zn0.7Fe2O4/PBZ 30% 30.01 4.005 54.74 0.133 4973.0
MgFe2O4/PBZ 70% 5.77 1.515 128.62 0.262 2380.9
ZnFe2O4/PBZ 70% 1.062 0.175 94.63 0.164 438.96
Mg0.7Zn0.3Fe2O4/PBZ 70% 12.61 1.947 77.58 0.154 2799.4
Mg0.3Zn0.7Fe2O4/PBZ 70% 12.84 1.626 62.93 0.126 2548.7

the studied samples as soft magnetic materials. From the Moreover, ­M r does not follow a linear trend. This
shape of the hysteresis loops and the saturation magneti- behavior may be because of the large radii of zinc which
zation values, the ferri-magnetic behavior is obvious too indirectly causes random remanent values [26].
[33]. In general, soft ferrimagnetic materials are very Moreover, in the composite samples, higher amounts of
useful in many industries and practical applications. The PBZ may increase ­Hc and decrease the saturation magneti-
small coercive force values permit easy magnetization zation ­Ms according to the following equation:
and demagnetization with little magnetic losses mak-
Ms = 𝜑 ms ;
ing the materials suitable for high-frequency uses [34].
From Table 3 also, it is observable that the total area of where M ­ s is expressed in terms of the volume fraction of
the loops has decreased significantly by introducing and particles (φ) and the saturation moment of a single parti-
increasing the polybenzoxazine into the samples (which cle ­(ms). The saturation magnetization decrease is logically
means a decrease in the magnetic losses), this is expected expected as mentioned above because of the non-mag-
upon adding a non-conducting polymer to ferrites caus- netic property of the PBZ. Similar observations have been
ing the M ­ s value to decrease and consequently the area reported many times by many researchers in the literature
of the curve will decrease. For more clarification, it is [12].
known that in a magnetic material with multiple domains, The squareness ratio ­R2 (= ­Mr/Ms) is a practically impor-
the process of creating or displacing a magnetic domain tant characteristic parameter of magnetic materials showing
requires energy (gained or lost in an uncompensable way). the ease by which the magnetization direction may change
This irreversibility is the reason behind the hysteresis in after a magnetic field is switched off. The squareness, as its
the M vs. H relationship. Therefore, it is logical that the name implies, measures how square the hysteresis loop is;
magnetic losses will decrease with decreasing the amount where for some applications, it should be as large as possi-
of magnetic material in the composites. ble, whereas for other applications, it should be as small as
In the Mg ferrite sample and its composites with PBZ, it ­ 2 is
possible. In the present study, it has been observed that R
can be observed that by increasing the zinc content to (0.3) less than 0.5 for all the samples suggesting that the samples
ratio, ­Ms has increased significantly, whereas by increasing
the zinc content to (0.7) ratio, ­Ms has slightly decreased
but still having higher values than the pure Mg ferrite sam-
ple, that may be attributed also to the matter of changing
Table 4  The assumed cation distribution formula according to cation
cationic distributions in different chemical compositions;
distribution preferences for the ferrite samples
where the magnetic properties of ferrites are known to
be significantly dependent on the cation distribution in The assumed distribution x value
A- and B- sites among other factors [3]. The ­Hc value has (Mg2+ Fe3+ )A [Mg2+ Fe3+ ]B ­O4 For x = 1
decreased by increasing zinc content in all samples due 𝛿 1−𝛿 1−𝛿 1+𝛿
For x = 0
(Zn2+ Fe3+ )A [Zn2+ Fe3+ ]B ­O4
to weakening the A–B interaction and the decrease in the 1−𝛿 1−𝛿 𝛿 1+𝛿
(Mg2+ Zn2+ Fe3+ )A [Mg2+ Fe3+ ]B ­O4 For x = 0.3
average particle size in agreement with the literature [26]. 𝛿 0.7 1−𝛿 0.3−𝛿 1+𝛿
(Zn0.3−𝛿 Fe1−𝛿 ) [Mg0.7 Zn𝛿 Fe1+𝛿 ] ­O4
2+ 3+ A 2+ 2+ 3+ B For x = 0.7

13
488 Page 10 of 11
Table 5  The experimental Sample
magnetic moment μB values
and the calculated cation
distribution according to these MgFe2O4
values
ZnFe2O4
Mg0.3Zn0.7Fe2O4
Mg0.7Zn0.3Fe2O4
are superparamagnetic and that the exchange-coupled inter-
action will not survive after removing the field [26, 35].
The magnetic moment μB is calculated experimentally
from the relation:
MA MS
𝜇B =
NA 𝛽
where ­MA is the molecular weight, N ­ A is Avogadro’s num-
ber, and β is the conversion factor to express the mag-
netic moment per atom in Bohr magnetons (its value is
9.27 × ­10–21 erg/gauss) [24].
A hypothetical cation distribution has been assumed to
give theoretically calculated values of net magnetic moment
identical to the measured magnetic moment estimated by
using the previous equation.
At first, a general form of the assumed cation distribution,
(Me2+ Fe3+ )A [Me2+ Fe3+ ]B ­O4
𝛿 1−𝛿 1−𝛿 1+𝛿
based on the site preferences of the ions, is shown in
Table 4.
Secondly, the values of the magnetic moment (experi-
mental) μB and the calculated cation distribution according
to these values are shown in Table 5.
According to this distribution, the Z ­ n2+ ions can exist
2+
on the A-site only when ­Mg ion content is (0.3), but for
higher ­Mg2+ content (0.7), some ­Zn2+ ions may migrate to
B-site preventing the existence of ­Mg2+ ions in A-site [36].
3 Conclusions
Nano-size powders of magnesium zinc ferrites have been
successfully synthesized by citrate precursor auto-com-
bustion and co-precipitation techniques. The FCC spinel
structure has been verified by the XRD patterns of all the
ferrite and composite samples studied. The crystallite size
estimated by using the XRD data has ranged from 17.2
to 31.5 nm in fair agreement with the average particle
size value calculated from the TEM data. In addition, it
is found that by increasing the Zn content, the crystalline
size (R) has decreased while the lattice parameter (a) has
increased in the samples prepared with auto-combustion
method. The benzoxazine monomer and polybenzoxazine
have been successfully prepared and the formation of both
of them has been confirmed by FTIR spectroscopy. The
13
M. M. Hussein et al.
Cation distribution which fits with the experimentally Experimentally
found magnetic moment calculated m (μB)
(Mg0.091Fe0.909)A[Mg0.909 ­Fe1.091]BO4 0.915
(Zn0.982 ­Fe0.982)A[Zn0.018Fe1.018]BO4 0.188
(Mg0.166Zn0.7Fe0.84)A[Mg0.134Fe1.16]BO4 1.663
(Zn0.131Fe0.831)A[Mg0.7Zn0.169Fe1.169]BO4 1.690
studied samples can be considered as soft magnetic mate-
rials which are believed to be very useful in many practi-
cal applications and industries. The small coercive force
values permit easy magnetization and demagnetization
with little magnetic losses making the materials suitable
for high-frequency uses and low loss applications too. M ­ s
has increased significantly in the Mg ferrite samples and
their composites with PBZ by increasing the zinc content.
The ­Hc value has decreased by increasing zinc content in
all samples. In the composite samples, higher amounts of
PBZ have led to an increase in H ­ c values and a decrease
in the ­Ms values. The squareness ratio ­R2 is less than 0.5
for all the samples suggesting that the samples are super-
paramagnetic. Because of containing PBZ, the studied
composites may exhibit very good resistance to chemicals,
safety concerning flammability, besides heat stability, they
may be excellent choices for manufacturing components
that may be exposed to high
temperatures and corrosive media.
Funding Not applicable.
Availability of data and material The datasets generated during and/or
analyzed during the current study are available from the corresponding
author on reasonable request.
Code availability Not applicable.
temperatures and corrosive media.
Declarations
Conflicts of interest Not applicable.
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