Journal of Alloys and Compounds 731 (2018) 279e287

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Introduction of Zn2þ in BaCoTiFe10O19 to tune electromagnetic

parameters and improve microwave absorption properties
Wenjia Xing a, b, Jing Chen a, b, Hua Wang a, b, Qingbo Fan a, b, Qin Lei a, b, Guangliang Xu b, *
a
State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang
621010, PR China
b
School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Zn2þ has been introduced to BaCoTiFe10O19 by sol-gel combustion method and the crystal system of
Received 13 December 2016 BaCoTiFe12O19 can be well preserved in the process. Through study of magnetic parameters, we pre-
Received in revised form liminarily expound the microwave-absorbing capacities, such as BaZn0.2Co0.8TiFe10O19 obtains preferable
31 July 2017
reflection loss (RL) with maximum saturation magnetization. Based on Debye dipolar relaxation of
Accepted 28 September 2017
Available online 7 October 2017
dielectric loss, the semicircles have been discussed in curves m"-m0 about magnetic loss for the first time.
The more semicircles curves m"-m0 have, the better RL is. The BaZn0.2Co0.8TiFe10O19 achieves a satisfactory
RL of 41.7 dB at 15.46 GHz with matching thickness of 2.1 mm. Its absorption bandwidth below 10 dB
Keywords:
BaCoTiFe10O19
is 7 GHz (10.47e17.47 GHz) and the absorption bandwidth below 20 dB is 4.63 GHz (11.7e16.33 GHz).
Sol-gel combustion The matching thickness of BaZn0.2Co0.8TiFe10O19 is smaller approximately 1 mm than that of BaCoTi-
Electromagnetic parameters Fe10O19. Therefore, investigation of the semicircle is significant to study magnetic loss and BaZn0.2-
Magnetic loss Co0.8TiFe10O19 could be a promising microwave-absorbing material.
Reflection loss © 2017 Elsevier B.V. All rights reserved.

1. Introduction wavelength upper and lower limits of bandwidth with r0 respec-

With applying electronic system to microwave communication
equipment, national defense, aerospace industry and so on, the
gigahertz (GHz) band has rapidly developed. Therefore, the elec-
tromagnetic absorbing materials require more favorable properties
[1e4]. Recently, broadening the absorption bandwidth, minimizing
reflection loss (RL) [5], minishing weight [6] and miniaturizing
particle size [7] have been studied extensively on absorbing ma-
terials. In practical application, the absorption bandwidth is one of
characteristics that's most attractive for a microwave absorbing
material. The static permeability m0 0 closely relates to theoretical
maximum frequency bandwidth, the equation as follows [8,9].
tively, Df is frequency bandwidth. Equation (1) implies that the
materials owning large m0 0 can obtain a broad absorbing bandwidth
with small d. In gigahertz (GHz) band, M-type barium ferrite
(BaFe12O19, BaM) is considered to be one of the most promising
microwave absorbing materials owing to the low cost, better sta-
bility, high natural resonant frequency (about 47.6 GHz) and
excellent microwave magnetic loss [10e14]. The main microwave
attenuation mechanism of BaM is magnetic loss. The magnetic loss
includes domain wall movement and magnetization of spin relax-
ation [15,16]. In addition, resonance frequency is closely related to
its magnetocrystalline anisotropy field, the relations as follows
[9,16].

8
>
< Dl≡l 2p2 m00 d
max  lmin 
jlnðr0 Þj (1)
>
:
Df fDl
8
where r0 is reflectivity, d is thickness, lmax and lmin are the < fr ¼ gHa
>
 
2Ms (2)
> 0
: m0 ¼ þ1
3Ha
* Corresponding author.
E-mail address: xuguangliangswust@163.com (G. Xu). For c-axis anisotropy, and

https://doi.org/10.1016/j.jallcom.2017.09.322
0925-8388/© 2017 Elsevier B.V. All rights reserved.
280 W. Xing et al. / Journal of Alloys and Compounds 731 (2018) 279e287

8 qffiffiffiffiffiffiffiffiffiffiffiffi min and calcined 4 h to obtain the BZCTM powders.

< fr ¼ g Hq H4
>
  (3) 2.2. Preparation of vector network analyzer's samples
>
: m0 ¼ Ms þ 1
0
2H4 Due to the paraffin wax (PW) almost no contribution to micro-
wave absorption [33], BZCTM was mixed with PW to investigate
for c-plane anisotropy. Where g is the gyromagnetic ratio, fr is the
microwave absorption properties. The composites were prepared
resonance frequency, Ha is the anisotropy field of c-axis anisotropy,
by mixing BZCTM powders with PW according to the mass ratio of
for c-plane anisotropy, Hq and Hf are out-of-plane anisotropy field
85:15. Subsequently, the mixture was dissolved in xylene and ul-
and in-plane anisotropy field respectively, m0 0 is the static perme- trasound for 30min. Finally, the solution was kept in the oven at
ability. Based on formula (2), the tremendous value Ha of BaM leads 56  C to remove the solvent completely. Under the 3.0 pa for 5 min,
to very high resonance frequency. Taking the place of Fe3þ with the mixture was pressed into a toroidal shape with inner diameter
other metal ions is a good way to adjust its anisotropy field of 3.00 mm, outer diameter of 7.00 mm and thickness is approxi-
[11,17,18], which is conducive to applying to different microwave mately 2.0 mm.
absorption band. For BaM, L. Du et al. [19] have verified that the
resonance frequency can be shifted to the X band (8e12.4 GHz)
2.3. Characterization of samples
through replacing Fe3þ with Co2þ and Ti4þ. In addition, So €zeri et al.
[20] have confirmed that the resonance frequency can be moved to
The phase composition of samples was studied by X-ray
the Ku band (12.4e18 GHz) when replacing some Fe3þ ions with
diffractometer (XRD, X'Pert PRO, PANalytical, the Netherland) with
Zn2þ, Co2þ, Mn2þ, Cu2þ, Ni2þ and Ti4þ. The magnetocrystalline
Cu Ka source (l ¼ 1.5406 Å). The size-distribution and morphology
anisotropy of BaCoxTixFe12-2xO19 can be tuned from axial to planar
were characterized by the field emission scanning electron micro-
with increasing x [17,21] and it means that the fr can be tuned to
scopy (FE-SEM, Zeiss Ultra 55, Germany). The magnetic hysteresis
lower frequency.
(MeH) loops of BZCTM powders were measured by the vibrating
Keeping the virtues of BaCoTiFe10O19, broadening its absorbing
sample magnetometer (VSM, BKT-4500Z, China) with the
band and tuning its resonance frequency are the focus of the study.
maximum magnetic field of 6 kOe. The relative permittivity
BaCoTiFe12O19 and BaZnTiFe12O19 possess similar saturation
(εr ¼ ε0 jε") and permeability (mr ¼ m0 jm") were measured by a
magnetization and coercivity, what's more, the RL curves of BaCo-
vector network analyzer (Agilent Technologies, E8363A, USA)
TiFe12O19 and BaZnTiFe12O19 have same variation trend [20]. Non-
adopted the coaxial measurements in the range of 0.5e18 GHz.
magnetic Zn2þ and Ti4þ can occupy some special sites to affect
the saturation magnetization [9,21e24]. Kong et al. [9] have
confirmed that the anisotropy field, Ha or Hf, would be weakened 3. Results and discussion
by putting Zn2þ ions in sites located Fe3þ ions. Therefore, BaZnxCo1-
The XRD patterns of BZCTM powders are shown in Fig. 1. All
xTiFe10O19 (BZCTM) could obtain relatively large saturation
magnetization (Ms) with the anisotropy field slightly changing. diffraction peaks are well consistent with the BaM (JCPDS Card No.
Based on Equation (2) or Equation (3), enlarging the Ms is beneficial 039-1433) and no other phase is detected. It means that intro-
to increase of m0 0, which can acquire a broad absorption bandwidth. ducing Zn2þ into BaCoTiFe10O19 not destroys its original phase [17].
In this paper, the electromagnetic parameters and microwave As shown in Table 1, the lattice constants of BZCTM have a little
absorbing properties of BZCTM are systemically studied with the fluctuation, which may be due to the radius value of Zn2þ
frequencies ranging from 0.5 to 18 GHz. (r2þ
Zn ¼ 0.74 Å) [22] very closes to that of Co
2þ
(r2þ
Co ¼ 0.745 Å)

In addition, for dielectric loss materials, Debye dipolar relaxa- [31e33]. what's more, the Co2þ [31,34,35] and Zn2þ [22,36] have
tion helps to enhance microwave absorption properties [25e27] different occupying sites.
and some studies [28,29] have proved ColeCole semicircles in For x ¼ 0, 0.1, 0.2, 0.4 and 0.8, the size and morphology of BZCTM
the plot of ε00 -ε0 . Compared with dielectric loss, the magnetic loss powders have been studied by FESEM. It can be seen from Fig. 2
maybe also has a similar conclusion. We will study the semicircles
in magnetic loss materials to establish some connections between
semicircle and RL.

2. Experimental

2.1. Preparation of samples

The powders of BZCTM (x ¼ 0, 0.1, 0.2, 0.4, 0.6 and 0.8) were
fabricated by the solegel combustion technique. The stoichiometric
Fe(NO3)3$9H2O (AR), Ba(NO3)2 (AR), Ti(OC4H9)4 (AR), Co(N-
O3)2$6H2O (AR) and Zn(NO3)2$6H2O (AR) were dissolved in 50 mL
deionized water with magnetic stirring to synthesize 0.005 mol
samples. After solutes completely dissolved, the 0.065 mol citric
acid (AR) was added into the solution and entirely dissolved. In
order to adjust the pH value to 7, ammonia solution (AR) was added
by dropwise with stirring. Subsequently, the adjusted solution was
heated up to 100  C with stirring to obtain dried gel. Keep on
heating, the dried gel would burn up in a self-propagating com-
bustion manner and some powders could be gained. These pow-
ders were heated up to 650  C with the heating rate 5  C/min and
pre-calcined 4 h, and then heated up to 1100  C with the speed 3  C/ Fig. 1. XRD patterns of BaZnxCo1-xTiFe10O19 composites.
 W. Xing et al. / Journal of Alloys and Compounds 731 (2018) 279e287 281

Table 1
Lattice parameters (a, c), ratio (c/a), and cell volume of BZCTM.

BZCTM(x) Lattice constants Ratio c/a Unit cell volume V (Å)

a ¼ b (Å) c (Å)

0 5.890 23.220 3.942275 697.61

0.1 5.892 23.204 3.938221 697.61
0.2 5.895 23.230 3.940628 699.13
0.4 5.895 23.205 3.936387 698.33
0.6 5.898 23.200 3.933537 698.91
0.8 5.897 23.22 3.937595 699.28

that the grains of BZCTM range from 150 to 600 nm and there is
agglomeration phenomenon caused by magneto dipole interaction
amongst magnetic particles [30]. There are some irregular
hexagonal-shape and majority of grains display irregular shape. In
addition, it is noted that BZCTM powders (x ¼ 0, 0.1, 0.2, 0.4 and 0.8)
have the same size distribution. The radius value of Zn2þ
(r2þ
Zn ¼ 0.74 Å) [22] is less 0.671% than that of Co
2þ 2þ
(rCo ¼ 0.745 Å)
2þ
[31e33], namely, introducing Zn would not severely change the
internal stress in crystal. It's beneficial to maintain the crystal size.
Therefore, for these samples, the particle size has no effect on
variation of samples' coercivity.
Fig. 3 shows the magnetic hysteresis loops of BZCTM powders
(x ¼ 0, 0.1, 0.2, 0.4, 0.6 and 0.8) and from Fig. 3 we can easily obtain
the trend of saturation magnetization (Ms) and coercivity (Hc). The
values of Ms increase with x from 0 to 0.2 and then gradually
decrease with increasing amount of Zn2þ. The Hc of BZCTM has little
change with x from 0 to 0.1 and then gradually increases with in-
crease of Zn2þ. Ms and Hc are relevant to the chemical element,
particle size and ion distribution in the oxygen vacancies. BaM has
five oxygen vacancies [20,23,31] where Fe3þ ions occupy sites. The
12k (octahedral site), 2a (octahedral site) and 2b (bipyramidal site)
have the same direction of spin that is defined as up, whereas, the
4f2 (octahedral site) and 4f1 (tetrahedral site) possess inverse spin
direction, marked with down. The Fe3þ ions occupy 12k, 2a, 2b, 4f1,
4f2 in the molar ratio of 6:1:1:2:2. The Co2þ ions preferentially
invade the 4f2 and 2b sites [31,34,35]. However some neutron
diffraction and Mo € ssbauer studies of BaZnxTixFe12-2xO19 have
showed that nearly all Zn2þ ions take up 4f1 sites at low doped
content [22,36]. The magnetic moment of Fe3þ and Co2þ are 5 mB
and 3.7 mB respectively [31], whereas, Zn2þ is non-magnetic
[20,22,23]. With Zn2þ ions increasing and Co2þ ions decreasing,
Fig. 3. Magnetic hysteresis loops of BaZnxCo1-xTiFe10O19 composites.
the Fe3þ ions located in 4f1 sites would enter 2b sites and 4f2 sites at
equal probability, which is equivalent to reducing the magnetic ions
of 4f1 sites. Therefore Ms increases with x from 0 to 0.2. On account
of weakening some exchange interactions [22,23] and breaking
magnetic collinearity [23] with x changing from 0.2 to 0.8, the Ms
gradually reduces. However, the 2b and 4f2 are mainly contributive
to the magnetic anisotropy of M-type barium ferrite [23,31,37], the
Co2þ has greater impact on magnetic anisotropy than Zn2þ. It's the
factor to enhance magnetic anisotropy. Therefore, the Hc of BZCTM
gradually increases.
To investigate the microwave absorption mechanism of BZCTM,
electromagnetic parameters are further studied with frequencies.
Generally, the real parts of permittivity (ε0 ) and permeability (m0 )
represent the energy of storage, however, the imaginary parts of
permittivity (ε") and permeability (m") represent inner dissipation
capability for incident electromagnetic wave. In Fig. 4a, when Zn2þ
ions increase, the ε0 gradually increases (x ¼ 0.6 is exception). The
ion polarizability of Zn2þ (a2þ¼2.09
Zn ) is bigger than that of Co2þ
(a2þ¼1.66
Co ) in oxides [38], which causes the increase of ε0 . The ε0 of
BaZn0.6Co0.4TiFe10O19 is anomaly and the phenomenon will be
further studied. All values of ε0 slightly rise with the increase of

Fig. 2. FE-SEM images of BaZnxCo1-xTiFe10O19composites with contents (x): (a) x ¼ 0, (b) x ¼ 0.1, (c) x ¼ 0.2, (d) x ¼ 0.4 and (e) x ¼ 0.8.
282 W. Xing et al. / Journal of Alloys and Compounds 731 (2018) 279e287
Fig. 4. Frequency dependence of electromagnetic parameters of samples with contents (x). (a) real part (ε0 ) and (b) imaginary part (ε00 ) of complex permittivity, (c) real part (m0 ) and
(d) imaginary part (m00 ) of complex permeability.
frequency. It can be seen from Fig. 4b that the values of ε" locate in
the range of 0e0.45. In the frequency ranging from 13 to 18 GHz,
the ε" of BaCoTiFe10O19 slowly increases, the ε" of BaZn0.1Co0.9Ti-
Fe10O19 slowly increases from 6 to 18 GHz, whereas the values ε" of
other samples present the increased, decreased and finally
increased tendency in 13e18 GHz. As shows in Fig. 4c, the m0 curves
of BZCTM initially decline with frequency ranging from 0.5 to 2 GH,
which attributes to limited speed of spin and domain wall move-
ment (displacement/rotation) [39]. With frequency continue
increasing, the value of m0 (x  0.6) slightly increases and then
decreases rapidly. It's favorable to the microwave surface imped-
ance match [40]. In 5e18 GHz, the point of m0 (x  0.6) that start to
decrease gradually shifts to higher frequency with substituting
Zn2þ. Some curves of m", with x  0.4, have an obvious and broad
peak in 5e18 GHz respectively and these peaks move to higher
frequency with doping Zn2þ, which means the resonance frequency
shifts to higher frequency (Fig. 4d). Based on (2), the fr moves to
higher conforming Ha would be strengthened with the amount
Zn2þ increasing. In 6e18 GHz, for x  0.4, the m" gets maximum at
some frequency and in same frequency, the corresponding m0 de-
creases fast (see Fig. 4c and d).
Based on electromagnetic wave propagation constant and
transmission line theory, microwave attenuation is a significant
element to an absorber. The attenuation constant a is defined as
follows [41e43].
pffiffiffi ! rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2pf
 ðm ε  m0 ε0 Þ þ ðm ε  m0 ε0 Þ2 þ ðm0 ε þ m ε0 Þ2
00 00 00 00 00 00
a¼
c main form of magnetic loss [28,41]. Fig. 5d shows that the values
(4)
where f is the electromagnetic wave frequency and c is the velocity
of electromagnetic waves in free space. Fig. 5a shows the a of
BZCTM versus frequency. It can be seen that the values of a slowly
increase at first. For x ¼ 0, x ¼ 0.1 and x ¼ 0.2, the a gradually
achieves maximum and then decreases. The a peaks of BZCTM
move to higher frequency with increase of x (x  0.2). Interestingly,
curves a and curves m" (see Fig. 4d) have the similar variation
tendency in the range of 5e18 GHz. The phenomenon reveals that
the microwave absorbing mechanism of these samples is mainly
magnetic loss in 5e18 GHz. What's more, the values a of BZCTM
composites are greater than those of the multiwalled carbon
nanotubes/Fe/Co/Ni NPs41 and core/shell-type FeNi NPs [42], which
indicates its absorbing property is better.
Furthermore, the dielectric loss tangents (tandε ¼ ε"/ε0 ) and the
magnetic loss tangents (tandm ¼ m"/m0 ) also are the significant
parameters to absorbing capacity. Fig. 5b and c show tandε and
tandm of BZCTM in different frequencies respectively. Compared
with ε" of BZCTM, the curves tandε of BZCTM have the same ten-
dency. The values of tandε fall into the range of 0e0.065. The curve
tandm of BZCTM (x  0.4) has an obvious peak (5e18 GHz)
respectively, which shifts toward higher frequency with the in-
crease of amount x. At low frequency, there is a small peak in all of
curves tandm. When x ranges from 0 to 0.6, the values of tandm are
huger than that of tandε and it reveals that the microwave ab-
sorption of composites is mainly from magnetic loss rather than
dielectric loss.
It is well known that exchange resonance, natural resonance and
eddy current effects compose the magnetic loss [44,45]. If the value
of m"(m0 )2(f)1 being nearly constant, the eddy current loss is the
m"(m0 )2(f)1 of BZCTM have sharp peaks in low frequency. The
curve m"(m0 )2(f)1 (x ¼ 0, 0.1, 0.2) has a broad peak in 5e18 GHz
respectively. There is very obvious fluctuation with frequency for
 W. Xing et al. / Journal of Alloys and Compounds 731 (2018) 279e287 283

Fig. 5. (a) attenuation constants of BaZnxCo1-xTiFe10O19 composites with frequency, (b) dielectric loss tangents (tandε) and (c) magnetic loss tangents (tandm) of samples with
contents (x), (d) the m"(m0 )2f 1 of BaZnxCo1-xTiFe10O19 composites.

x  0.6. It means that the eddy current loss is not the primary  2
magnetic loss form. The values m"(m0 )2(f)1 are almost constant 00 2 Bm
m0 þ m ¼
2
(8)
ranging from 6 to 18 GHz with x ¼ 0.8, which means that eddy m 0 Hm
current loss is the prime form of magnetic loss.
Therefore, the curves of m"m0 would be similar rotundity. It is
In the alternating magnetic field, the magnetic field and mag-
netic induction intensity are expressed as follows: clearly seen in Fig. 6 that for x ¼ 0 and 0.1, the curve m"m0 of
BZCTM composites has three distorted semicircles, for x ¼ 0.4
( and 0.6, there are two distorted semicircles respectively, whereas
~ ¼ Hm expðjutÞ
H four semicircles appear in the curve m"m0 with x ¼ 0.2. It can be
  (5)
~ ¼ Bm exp j ut  dm
B seen totally disordered curves with x ¼ 0.8. Therefore, BaZn0.2-
Co0.8TiFe10O19 could own best absorption capacity than other
where dm is magnetic loss angle, Hm and Bm are the amplitudes of samples.
magnetic field and magnetic induction intensity respectively. The To better illustrate the semicircles of curves m"m0 , Fig. 7 shows
complex permeability mrcan be written as: 3D diagram about the relation of f, m" and m0 of BaZn0.2Co0.8Ti-
Fe10O19. The 3D curve is downward tortuosity with frequency. The
!   three projections have been illustrated as earlier. In 8e16 GHz, the
~
B Bm  
mr ¼ ¼ exp jdm curves of m" and m0 have a peak respectively, what's more, the severe
~
m0 H m0 Hm tortuosity of 3D curve is also located in the frequency zone. A dis-
    (6)
torted semicircle represents a kind of magnetic loss mechanism.
Bm Bm 00
¼ cos dm  j sin dm ¼ m0  jm The more distorted semicircles mean there are multiple the mag-
m0 Hm m0 Hm netic loss mechanisms, which is beneficial to enhance the reflection
loss. We will continue to explore the distorted semicircle in next
where m0 is permeability in free space, we can deduce from Equa-
work.
tion (6) that
The reflection loss (RL) parameter is studied in detail to reveal
8   the property of microwave absorption. There is strongly positive
>
> 0 Bm correlation between absorbing ability and RL, namely, the smaller
>
< m ¼ cos dm
m 0 Hm value RL makes a better absorbing effect. Based on transmission line
  (7)
> 00
> Bm theory, the value of RL can be computed utilizing relative complex
>
:m ¼ sin dm permittivity and permeability. On the condition of giving frequency
m0 Hm
and thickness, the RL value can be calculated by following equations
From Equation (7), we can further deduce that [11,16,17,28,32,46].
284 W. Xing et al. / Journal of Alloys and Compounds 731 (2018) 279e287

Fig. 6. The curves m"-m0 of BaZnxCo1-xTiFe10O19 composites.

Fig. 7. Three-dimensional diagram of BaZn0.2Co0.8TiFe10O19 with f, m" and m0 .

8 rffiffiffiffiffi    where l is the wavelength in the materials at fm, fm and tcal

m are the
>
> mr 2pfd pffiffiffiffiffiffiffiffiffi peak frequency and the matching thickness of maximum micro-
< Zin ¼ εr tanh j
>
c
mr εr
wave absorptions.
(9)
>
> ðZ  1Þ To illuminate the elements affecting microwave absorption
>
: RL ¼ 20 log in
ðZ þ 1Þ
properties, the curves RL of BZCTM composites are illustrated in
in
Fig. 8. Fig. 8a shows the curves RL of BZCTM-paraffin with thickness
where Zin is the inputting impedance of absorber, mr and εr are of 2.0 mm in the range of 0.5e18 GHz. In the range of 10e18 GHz,
relative complex permeability and permittivity respectively, d is the the value of RL decreases with x ranging from 0 to 0.2, and then
thickness of absorber, f is the electromagnetic wave frequency and c increases within x ranging from 0.2 to 0.8. It can be noticed that
is the velocity of electromagnetic waves in free space. BaZn0.1Co0.9TiFe10O19 composite possesses a mostly broad band-
If the thickness of absorber (tm) is suitable, the minimal re- width below 10 dB (means 90% absorption) ranging from 9.7 to
flections can be obtained at the peak frequency [47e49]. 17.47 GHz and the bandwidth of BaZn0.2Co0.8TiFe10O19
below 10 dB ranges from 10.8 to 17.73 GHz. However, other
nl nc samples manifest relatively poor microwave attenuation with
t cal
m ¼ ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  ðn ¼ 1; 3; 5; …Þ (10) thickness of 2.0 mm. Compared with BaCoTiFe10O19, the points of
4 4f m jεr jjmr j
minimum values RL of BaZn0.1Co0.9TiFe10O19 and BaZn0.2Co0.8Ti-
Fe10O19 shift to higher frequency in accordance with the trend of
 W. Xing et al. / Journal of Alloys and Compounds 731 (2018) 279e287
Fig. 8. (a) RL for different samples (x ¼ 0e0.8) with a thickness of 2.0 mm, (b) RL, simulated thickness and calculated thickness for BaCoTiFe10O19 with different thickness, (c) RL,
simulated thickness and calculated thickness for BaZn0.1Co0.9TiFe10O19 with different thickness, (d) RL, simulated thickness and calculated thickness for BaZn0.2Co0.8TiFe10O19 with
different thickness.
curves a (see Fig. 5a). For x ¼ 0.8, the RL mainly derives from the
eddy current loss (6e18 GHz) and the RL value is not obvious, which
means the eddy current loss is very little for BaM. BaZn0.1Co0.9Ti-
Fe10O19 and BaZn0.2Co0.8TiFe10O19 achieve favorable absorption
properties.
Fig. 8b displays curves RL, simulated thickness (d) and calcu-
lated thickness (tcal
m ) of BaCoTiFe10O19. When thickness increases to
3.2 mm, it can obtain a minimum RL (43 dB) at f ¼ 8.55 GHz.
What's more, its absorbing bandwidth below 10 dB ranges from
6.8 to 12.6 GHz. When d equals to 3.0 mm, the absorption band-
width below 20 dB reaches widest being 3.6 GHz (8.6e12.2 GHz).
Unfortunately, the thickness is a bit thick, which is opposed to
lightweight. With thickness increasing, the optimum frequency of
reflection loss move to lower. To better demonstrating the phe-
nomenon, Fig. 8b shows the calculated thickness (tcal m ) and simu-
lated thickness (d). The values of d are directly gained from the
curves RL. The tcal
m and d are almost consistent.
Fig. 8c shows the curves RL, simulated thickness (d) and calcu-
lated thickness (tcal
m ) of BaZn0.1Co0.9TiFe10O19. RL value reaches
minimum (45 dB) at f ¼ 10.825 GHz with d ¼ 2.1 mm. For
d ¼ 2.0 mm, the absorption bandwidth below 10 dB ranges from
9.7 to 17.47 GHz, which is the widest bandwidth below 10 dB.
However, the absorption bandwidth below 20 dB is too narrow.
Form the Fig. 8c, the tcal
m and d are approximate match. There are
some peaks in lower frequency, which due to the domain wall
motion [15,50,51]. However, other samples have no peak in lower
285
frequency, which maybe the peak being weak or covered by behind
peak.
Fig. 8d shows the curves RL, simulated thickness (d) and
calculated thickness (tcal
m ) of BaZn0.2Co0.8TiFe10O19. RL value reaches
minimum (41.7 dB) at f ¼ 15.46 GHz with d ¼ 2.1 mm. The ab-
sorption bandwidth below 10 dB is as wide as 7 GHz
(10.47e17.47 GHz) and the absorption bandwidth below 20 dB is
4.63 GHz (11.7e16.33 GHz). Compared with BaCoTiFe10O19, the
optimal matching thickness decreases about 1 mm and the
absorbing frequency shifts to higher. Form the Fig. 8d, it is obvious
that the tcal
m and d are approximate match.
To better reveal microwave absorption properties, Fig. 9 displays
3D RL diagram of BaZn0.2Co0.8TiFe10O19 with different frequencies
and thicknesses. There is obvious that the high absorbing intensity
area is located in the zone made up by low thickness and high
frequency. Moreover, the shaded area possesses a better absorption
curve, which moves to lower frequency with increasing thickness.
Thickness being about 2 mm, we can suppose that the absorbing
capability is fine in the range of 10.5e18 GHz.
4. Conclusions
BZCTM were successfully synthesized via the sol-gel combus-
tion method. The crystal system of BaFe12O19 can be well preserved
in the process. Due to Zn2þ and Co2þ preferentially occupying
different sites, BaZn0.2Co0.8TiFe10O19 attains relatively larger Ms
286 W. Xing et al. / Journal of Alloys and Compounds 731 (2018) 279e287
Fig. 9. Three-dimensional RL of BaZn0.2Co0.8TiFe10O19.
with the Hc slightly augmenting, which is beneficial to improve
absorption property. We have researched the electromagnetic pa-
rameters and revealed that the microwave absorbing mechanism of
BZCTM is major magnetic loss. The relations have been summarized
between doped content of Zn2þ and absorption capacity. The
BaZn0.1Co0.9TiFe10O19 reaches minimum RL of 45 dB at 10.825 GHz
with d ¼ 2.1 mm. For d ¼ 2.0 mm, the absorption bandwidth
below 10 dB ranges from 9.7 to 17.47 GHz. For
BaZn0.2Co0.8TiFe10O19 at d ¼ 2.1 mm, its absorbing bandwidth
below 10 dB is approximately 7 GHz (10.47e17.47 GHz) and the
absorption bandwidth below 20 dB is 4.63 GHz (11.7e16.33 GHz).
These advantages render the BaZn0.2Co0.8TiFe10O19 as a promising
potential microwave-absorbing material. Based on Debye dipolar
relaxation of dielectric loss, the semicircles have been discussed in
curves m"m0 about magnetic loss for the first time. A distorted
semicircle represents a kind of magnetic loss mechanism. The more
distorted semicircles mean there are multiple the magnetic loss
mechanisms, which is beneficial to enhance the reflection loss. We
will continue to explore the distorted semicircle in next work.
Therefore, the more semicircles curves m"-m0 have, the better RL is.
What's more, the exploration of semicircle is a vital significance to
study magnetic loss.
Acknowledgment
This work is supported by the key scientific research projects of
Southwest university of science and technology (No. 15zx2101) and
the key scientific research projects of Southwest university of sci-
ence and technology (No. 17zx910201).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.jallcom.2017.09.322.
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