Egyptian Journal of Petroleum 28 (2019) 361–369

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Lithium ferrite (LiFe5O8)/polymethyl methacrylate (PMMA)

nano-composite used in high dielectric constant capacitor and
electromagnetic applications
Gamal M. Nasr, Emad Mousa, Mariam M. Haroun
Physics Department, Faculty of Science, Cairo University, Egypt

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

Article history: Poly methyl methacrylate/ Lithium ferrite nano-composites have been prepared by solution mixing pro-
Received 30 April 2019 cess. The electrical conductivity and dielectric properties of these prepared nano-composite have been
Revised 2 July 2019 investigated in the frequency range 102–106 Hz at different LiFe5O8 concentrations from 0 vol% to
Accepted 7 August 2019
25 vol%. The prepared samples are studied by thermal gravimetric analysis (TGA) and X-ray diffraction
Available online 21 August 2019
(XRD). Moreover, the magnetic properties of these nano-composites are investigated through vibrating
sample magnetometer studies. XRD spectral investigation revealed that the structural of PMMA and its
Keywords:
chemical characterization are appreciably affected by mixed lithium ferrite filler. The thermal stability
PMMA
Dielectric constant
of the PMMA matrix was found to increase appreciably by LiFe5O8 loading. The (I-V) characteristic of
AC conductivity these nano-composites are in very good agreement with the non-linearity predicted by Kaiser et al.
Magnetization model. The effective dielectric constant is studied through different proposed models. Saturation magne-
Nano-composites tization of 10.05 emu/g is achieved for PMMA sample loaded with 25 vol% of LiFe5O8 particles.
Li-Ferrite Ó 2019 Production and hosting by Elsevier B.V. on behalf of Egyptian Petroleum Research Institute. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Nano-crystalline materials are recently the center of attention
due to their enormous applications and interesting properties.
The properties of nanomaterials are remarkably different than that
of their bulk counterpart. Ferrite nanoparticles are interesting due
to their different technological applications. Lithium Ferrite have
received considerable interest among scientific communities for
microwave applications such as isolators, circulars, gyrators, phase
shifters and memory cores [1–4].
Moreover, Lithium ferrite can be used in a lot of applications
such as cathodes in rechargeable lithium batteries, in high-
capacity batteries, in electrochromic displays and used as strong
oxidizing agents [5–9]. Due to low fabrication cost of lithium Fer-
rite, it can be used in mass scale microwave devices instead of the
more expensive yttrium iron garnet (YIG) [10]. Lithium Ferrite
belong to the soft spinel ferrite materials with a square hysteresis
loop, high Curie temperature and saturation magnetization.
Lithium Ferrite used as filler material to enhance the properties
of the usage polymer by forming a composite. The easy manufac-
Peer review under responsibility of Egyptian Petroleum Research Institute.
E-mail address: emad@sci.cu.edu.eg (E. Mousa)
turing polymeric materials at lower cost is the main reason behind
increasing the importance of these materials.
One of the major types of functional polymers is poly methyl
methacrylate which have many excellent properties [11–13].
Because of the crystal– amorphous interfacial effect of PMMA, it
represents a numerous physical properties [14]. PMMA is a trans-
parent thermoplastic polymer with dielectric constant (3 4:9Þ and
low dielectric losses over wide frequency range at room tempera-
ture [15].
One of the ways that is used to develop the chemical and phys-
ical properties of polymer materials is by introducing an electri-
cally conductive filler [16–18]. Teixeira [19], prepared a
composite material by dispersing lithium ferrite particles in a
styrene-b-isoprene-b-styrene (SIS) copolymer. He studied the
dielectric properties of the composites in the frequency range
between 10-1 and 106 Hz, and as a function of the temperature
between 200 and 400 K. The results show that as the particle con-
centration increases the electrical conductivity increases.
A dielectric spectroscopic studies on (PMMA/ CaCu3Ti4O12)
composites was conducted by Thomas [20]. He found that with
increasing the weight percentage of CaCu3Ti4O12 (0–40)%, both
the dielectric constant and losses increase. Applications in estab-
lished and cutting-edge terahertz frequency systems needs materi-
als with low loss and high dielectric constant [21]. The different

https://doi.org/10.1016/j.ejpe.2019.08.002
1110-0621/Ó 2019 Production and hosting by Elsevier B.V. on behalf of Egyptian Petroleum Research Institute.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
362 G.M. Nasr et al. / Egyptian Journal of Petroleum 28 (2019) 361–369

applications are not limited to laboratory systems, but includes
aerospace, automotive, communications, defence, domestic, medi-
cal, and marine applications [22–26].
Our goals in this study are to elucidate the effect of lithium fer-
rite (cubic spinel) as a filler introduced into polymethyl methacry-
late matrix and to investigate the different conduction mechanism
in these nano-composite via the measurements of the AC electrical
properties at different frequencies as well as the DC electrical
properties.
These measurements enable us to study the molecular dynamic
of a composite containing lithium ferrite particles embedded in the
PMMA matrix. Moreover, Jonscher’s law [27] will be used to ana-
lyze the conductivity dispersion phenomenon in the tested com-
posite. The structural properties of lithium ferrite and lithium
ferrite/ polymethyl methacrylate have been investigated by XRD.
Moreover, the prepared nano-composites samples were studied
by thermal gravimetric analysis (TGA) to elucidate the effect of fer-
rite doping on the thermal stability as well as the glass transition
temperature of the PMMA composites. Some light was also thrown
on the DC electrical properties as well as the magnetic properties
of the ferrite/ polymer nano-composites.
2. Experimental technique
2.1. Preparation of PMMA (matrix), using Benzoyl Peroxide (casting)
The purified monomer MMA (12.94) mL with (Mw = 100.12 g/-
mol) and density equal to 1.18 gm/cm3 with purity 99% supplied
from (RESERCH-LABFINE CHEM INDUSTRIES) Company, was taken
in a polymerization tube and (0.0485) g of Benzoyl Peroxide which
act as catalyst was added to accelerate the polymerization in the
polymerization reaction.
The polymerization tube was then taken in water bath at 333–
343 K in an oven for three days. A hard viscous polymer was
obtained after three days of heat treatment [28]. A definite poly-
merized weight was dissolved in chloroform until totally dissolv-
ing of PMMA in which the solution reach viscous state and then
transferred into buttery dish. The viscous polymer solution was left
in air (at room temperature 300 K) for one day. This led to get rid of
chloroform.
2.2. Preparation of LiFe5O8 (filler) by auto-combustion citrate method
Lithium ferrite LiFe5O8 was synthesized using citrate –nitrate
auto-combustion method. Ultra-pure ferric nitrate Fe(NO3)39H2O
was dissolved in water with lithium carbonate (Li2CO3) in stoichio-
metric ratios. Citric acid was then added in a ratio equivalent to
sum of molar ratios of the reactant and the PH was adjusted to
7–8 PH units. The mixture was then heated on a hot plate at
393 K until self-ignition took place. The obtained powder was fur-
ther heated at 473 K for one hour to complete the reaction and for
drying [29].
300 K) for one day leads to the formation of composite’s thickness
from 0.03 to 0.07 cm.
3. Measurement analyses
X-ray diffraction patterns were obtained with a Brucker Weis
D8 diffractometer (Cu Ka radiation, k = 1.5405 Å at 40 kV and
40 mA.
For the electrical measurements, the samples were sandwiched
into two stainless steel electrodes of parallel plate capacitor. The
measurements were carried out using LCR-bridge (type HIOKI
3532 – 50 LCR HiTESTER) in the frequency range from 10-1 up to
106 Hz, with increasing temperature (5° steps) from 25° up to
120 °C. The temperature control was performed within 1 °C using
a regulated electric oven. The dielectric permittivity was calculated
using the relation:
0
e ¼ Cd=eo A ð1Þ
where C is the measured value of capacitance of the sample, d is the
thichness, A is the surface area and eo is the electric permittivity of
air (8.85 * 10-12 F/m). Magnetic measurements were performed at
room temperature (300 K) by applying 20 K Gauss magnetic field
using vibrating sample magnetometer (Model: Lake Shore ISO
9001 certified company 7410-USA). DC electrical properties of the
samples are measured by using the four probe technique. The elec-
trical contact were made using silver paste. An electrometer
(KEITHLEY 485 AUTORANGING PICOAMMETER) was used to detect
the samples current.
4. Results and discussions
4.1. Thermal gravimetric analysis
Thermal stability of PMMA/LiFe5O8 is tested by thermo gravi-
metric analysis (TGA). Fig. 1 shows the TGA thermograph of differ-
ent weight ratio of LiFe5O8 of PMMA/LiFe5O8 composites at a
heating rate 10 K=min: under Nitrogen atmosphere. It is observed
that the pure PMMA losses 50% of weight at the decomposition
temperature (T d Þ of 608 K on the contrary upon loading by LiFe5O8
(1, 3, 5, 15 and 25%) particles. The samples loss the same weight at
T d ¼ ð600; 604; 614; 626:4 and 630:86 KÞ respectively.
The chair yields of the PMMA and PMMA loaded with different
LiFe5O8 contents at 771.8 K, are (0.0, 0.29, 2.62, 3.27, 11.98 and
18.47%). Comparing the values with mass quantities of (lithium
ferrite) LiFe5O8 impeded in the PMMA matrix indicates small dif-
ference between the mass percentage of lithium ferrite and that
obtained by TGA, which means that the particles distribution in
95 0%
1%
75 3%
weight losses %

2.3. Preparation of the composite PMMA/LiFe5O8 using Devikala 5%

25 25%
method [24] 55 45 15%
15 15%
25%
35
5%
A definite quantity of PMMA was dissolved in chloroform till it 35 25 5 3%
1%
produce a viscous solution of PMMA. This was followed by the 15 -5
0%

addition of a known quantity of prepared LiFe5O8 and then it was 5 400 450 500
15
made into a paste in an agate mortar [30]. After that the viscous -5
composite was poured in a petri dish followed by using a pestle 640 690 740
-5
to let the ferrite distribute through the viscous PMMA carefully 270 370 470 570 670 770
which is taking only a few seconds. A different concentrations of Temp.(K)
LiFe5O8 (filler) are used such as (1%, 3%, 5%, 15% and 25%). After
that the composite solution is subjected into air (at room temp. Fig. 1. Shows the TGA of the composites PMMA/ LiFe5O8 at different filler contents.
 G.M. Nasr et al. / Egyptian Journal of Petroleum 28 (2019) 361–369
PMMA network is not completely uniform and this observation
was also detected by Teixeira (2014) [31], for the composite (LiFe5-
O8/SIS).
It can be explained in such a way that there is a strong interac-
tion between LiFe5O8 and PMMA matrix. Leads to difficult thermal
degradation of PMMA. Thus, the thermal stability of PMMA rela-
tively increase by LiFe5O8 loading.
4.2. X-ray diffraction structural characterization
X-ray diffraction analysis (XRD) of all samples were carried out
using Brucker Weis D8 diffractometer and Cu-Ka (k = 1.5406 Å)
radiation, 40 kV and 40 mA which was made in Germany.
Fig. 2a shows the XRD pattern of all loaded PMMA where Fig. 2b
shows the XRD pattern of pure LiFe5O8 material. The diffraction
pattern that is presented in figure (2b) shows all peaks assigned
to lithium ferrite single crystal phase compared to [00–082–
1436] ICCD card with spinel cubic structure as compared with lit-
erature [32].
The diffraction patterns indicate that the sample has cubic spi-
nel crystal structure for the pure (LiFe5O8) with space group P4132
as also observed by Patil et al. [33]. The lattice parameters were
calculated for the cubic phase using the following relation:
2 2 2 1=2
a ¼ dðh þ k þ l Þ
where (a) is the lattice parameter and (h k l) are miller indices.
The lattice parameters (a), average crystalline size (R) and the
surface area (S) of spinel ferrite crystalline can be calculated and
are tabulated in Table 1 using the full-width at half –maximum
(FWHM) of the prominent reflection (2 2 0), (3 1 1) and (4 4 0)
using Scherer’s equation, and the X-ray density (Dx ) was calculated
using the relation (4) and tabulated in Table 1.
R ¼ ð0:89kÞ=ðbcoshÞ
Dx ¼ ðZMÞ=ðNVÞ
S ¼ 6000=ðRDxÞ
where k is the incident wavelength of the Cu Ka radiation of the
XRD, b is the peak width at mid height, and h is the angle consid-
ered, Z  8 for spinel , M is the molecular mass of the composition,
N is the Avogadro’s number, and V is the unit cell volume. As shown
from Table 1 that both R value and S value is in good agreement
with literature [32]. To investigate the effect of LiFe5O8 loading in
Fig. 2. (a and b) XRD for (Li-Ferrite) and different contents of (Li-Ferrite) impeded in PMMA respectively.
363
Table 1
Crystallographic structural data of Lithium Ferrite.
Lattice parameter Å (a) Crystalline Surface area Density
size nm (R) m2/g (S) gm/cm3 (Dx)
8.3313 38 33.4 4.7
the amorphous PMMA polymer chain, the XRD spectra for pure
LiFe5O8, PMMA and PMMA/ LiFe5O8 nano-composite were analyzed
as shown in Fig. 2 a-b. The XRD pattern of PMMA/ LiFe5O8 shows
unique characterization of composite indicating the co-existence
of both crystalline and amorphous region with pronounced peak
at about 37° and 63° (2hÞ especially for higher filler loading. These
pronounced peaks are mainly due to the introducing of ferrite par-
ticles into the polymer matrix chains. The loading of the filler par-
ticles into the polymer matrix alters both the broadness and
intensity of the existing original peaks. The increase in broadness
or reduction in intensity indicates the change in the crystallinity
of the pristine polymer, indicating the orderly alignment of polymer
chains by chain folding or by the formation of single or multiple
helices [34]. The average polymer chain separation d can be calcu-
lated by using equation [34]:
d ¼ 5k=8sinh ð6Þ
ð2Þ
where h is the diffraction angle at the maximum intensity position
of the XRD, so the average chain separation for PMMA/LiFe5O8 com-
posites was estimated to be around 4.45 Å as shown in Table 2. This
an un-adulatory behavior could be interpreted on the bases of two
competing processes, polymer chain segregation effects and filler
aggregation.
ð3Þ 4.3. Dielectric properties of PMMA/Ferrite composites
ð4Þ Owing to their outstanding electrical, magnetic and optical
properties, inorganic-polymeric materials have been popularized
ð5Þ globally. The easily manufacturing at lower cost of these materials
was the reason of the importance of such materials. Poly methyl
methacrylate (PMMA) have many desirable properties [11,12,35].
Due to its crystal amorphous interfacial effect [36], it represents
numerous physical properties. The value of the dielectric constant
of PMMA at room temperature is approximately (3–4.9) [34].
Meanwhile, PMMA possess a low dielectric loss over a wide range
of frequencies [37].
364 G.M. Nasr et al. / Egyptian Journal of Petroleum 28 (2019) 361–369

Table 2
The chain separation of the composites PMMA/ LiFe5O8 at different filler volume fraction.

LiFe5O8 concentration 0 0.0182 0.0283 0.0852 0.134

Chain separation (d) Å 4.48 4.87 4.37 3.76 4.78

We try in this section to present a study on the effect of Lithium And the imaginary part of e ðxÞ is given as:
Ferrite (LiFe5O8) filler in PMMA matrix, with the aid to elucidate
es  e1
and study the dependence of the dielectric properties and DC elec- e00 ðxÞ ¼ ðes  e1 Þ þ ð11Þ
1 þ ðx2 s2 Þ
trical properties on both frequency and temperature changes
respectively. where es and e1 stands for the low and high frequencies values of
e ðxÞ withx = 2pf , f is the measured frequency and s is the relax-
4.4. Theory [34] 0
ation time. The dielectric constant and loss (e & e00 ) both have sig-
nificant physical meaning according to statistical mechanics,
For polymeric material and its composites, the dielectric analy- where e0 refers to the energy stored per cycle and e00 stands for
sis data have a greater importance when performed in particular the energy loss per cycle.
frequency ranges. The complex dielectric constant e ðxÞ is an Moreover, the AC electrical conductivity rAC is given by:
!
important factor correlating the electric field E (x) and the result-
ing polarization (P) of the matrix [38,39] that could be one of the rAC ¼ eo x e00 ð12Þ
form
! ! 4.5. Dielectric measurements
P ¼ ðe ðxÞ  1Þeo E ðxÞ ð7Þ
Fig. 3a and b show the frequency dependent dielectric behavior
where x is the angular frequency.
of both real and imaginary parts of the complex permittivity of
Havriliak-Negami [40,41], relates the complex dielectric per-
PMMA/ LiFe5O8 composite at room temperature.
mittivity with the oscillation in an AC field by the equation
Due to the grain boundaries which possess a high dielectric con-
es  e1
e ðxÞ ¼ e1 þ c d
; 0c & d1 ð8Þ stant, the dielectric constant at low frequency range have a high
ð1 þ ðixsÞ Þ value. Meanwhile, a high frequency dielectric constant results from
grains which have low dielectric constant [43]. At high frequencies,
Here c (=1) and d (=1) are empirical parameters. This provides the
the polarization decreases due to accumulation of charge that are
Deby relaxation law, in the case d = 1, c – 1 one get the so- called
not capable to diffuse in the field direction. The dielectric constant
cole–cole equation [42].
increases slightly with addition of LiFe5O8 particles.
For the frequency- dependent dielectric permittivity, The Deby
formula is given as:
4.6. Effective dielectric constant
es  e1
e  ðxÞ ¼ e1 þ ð9Þ
1 þ ðixsÞ With varied levels of agreements between the theoretical and
The real part of e ðxÞis shown as: experimental values many researchers try to predict the macro-
scopic properties of a composite system using the properties of
es  e1
e0 ðxÞ ¼ e1 þ ð10Þ its constituents. Table 3 shows the room temperature dielectric
1 þ ð x2 s 2 Þ constant of the PMMA/LiFe5O8 composite at 5 MHz (experimental)

Fig. 3. (a and b) Dielectric constant and dielectric losses for different weight % of LiFe5O8 at room temperature, respectively.
 G.M. Nasr et al. / Egyptian Journal of Petroleum 28 (2019) 361–369 365

Table 3
Dielectric constant of the PMMA/ LiFe5O8 composites at 5 MHz (experimental) for different LiFe5O8 loading at room temperature.

Volume fraction of filler 0 0.00615 0.0182 0.0283 0.0852 0.134

0
e 3.40 3.59 3.86 4.09 4.35 4.95

for different volume fraction of LiFe5O8. The dielectric constant cal- 4.6.4. Lichtenecker model based on Wiener limits [49]
culated based on various models [44–50], for comparison they are For real composite, Wiener proposed that the effective dielec-
included in the same Fig. 4. tric constant follows the following limits,
The equations used to calculate the effective dielectric constant
 1  0 1 1
(e0 Þ of the composites are as follow u1 : e01 þ u2 : e2 6 e0eff 6 ðu1 : e01 þ u2 : e02 Þ ð16Þ

This limit are not physically proven but only assumption.

4.6.1. Furukawa model [47]
Lichtenecker take into his account Wiener limits and proposed a
formula [48]:
h

i
 u
e0eff ¼ 1 þ 2uf = 1  uf  e01 ð13Þ u1  e01 þ u2  e2
e eff ¼

0
    1u ð17Þ
where e0 1 denotes the dielectric constant of the polymer matrix and u1  e01 1 þ u2  e02 1
uf volume fraction of the filler. Spherical and uniformly dispersed
where u is the relative weight of parallel connection and (1-u) is the
ferrite particles in PMMA are assumed by this model (Furukawa
relative weight of series connection, u1 and u2 ððu1 þ u2 = 1) are
model).
the volume fraction of the dielectric (1) (polymer matrix) and
dielectric (2) (filler particles) respectively.
4.6.2. Series mixing formula [48] A plot showing the variation of the above models is shown in
Fig. 4. Furukawa model presented in Fig. 4 is not applicable for



 uf < 0:085: The series mixing formula is in disagreement with
1=e0eff ¼ uf =e02 þ 1  uf =e01 ð14Þ the experimental values. The Lichtnecker logarithmic Eq. (15) con-
siders the composites as random mixture of nearly spherical inclu-
where e0 eff and e0 2 are the dielectric constant of the composites sions. The calculated values (in this model) are valid for composites
and filler respectively. with low filler loading and shows a slight deviation at higher filler
loading. This modified equation including a fitting factor n, which
4.6.3. Modified Lichtnecker equation[48] represents the interaction between the filler and the matrix. Licht-
necker model based on Wiener limits (Eq. (16)) gives a good fitting
of its effective dielectric constant with that measured empirically
loge0eff ¼ loge01 þ uf ð1  nÞlogðe02 =e01 Þ ð15Þ on the whole filler loading range (Fig. 4). The appropriate value
of u which gives a good fitting is (u = 0.005) which mean that the
The composites were considered as a random mixture of nearly relative weight of series connection is more favored in these
spherical inclusions as proposed by this model.
composites.

4.7. DC electrical properties of LiFe5O8/PMMA composites:

In recent years many researchers [50–52] gave a considerable

attention to the nonlinear electrical conductivity behavior of
nanoparticles modified polymers and several efforts have been car-
ried out to elucidate the current –voltage characteristics of such
composites.
In this section, the I-V characteristics of a series of loaded
PMMA /Lithium Ferrite are measured at constant temperature
(373 K) to investigate the transport behavior in these composites.
Moreover, all the nonlinear I-V curves will be fitted by Kaiser
et al expression [54].

4.7.1. I-V characteristics

Recently, Kaiser et al. [53] proposed generic expression
(extended fluctuation – induced tunneling (FIT) and thermal exci-
tation model [54]) for nonlinear I-V characteristics based on
numerical calculations for metallic conduction interrupted by
small barriers.

4.7.2. Kaiser expression [55]

In terms of the FIT model [54], Kaiser et al. [53–55], proposed a
generic expression, which can give a good description to the
Fig. 4. Dielectric constant of the PMMA/LiFe5O8 composite at 5 MHz (experimental changing shape of nonlinear I-V characteristics in polymer-
and theoretical) for different volume fraction. composites by using numerical calculations of the current
366 G.M. Nasr et al. / Egyptian Journal of Petroleum 28 (2019) 361–369

fluctuation-assisted tunneling through conduction barriers and

thermal activation over the barriers of the form

C l expV=V s
C ¼ I=V ¼ ð18Þ
1 þ m½exp VVs  1

where C l , m andV s are parameters. C l is the temperature dependent

low field (V ! 0Þ conductance. The parameters m = CC l (m < 1) yields
h

a decrease of C l below the exponential increase at higher voltage V

(C h is the saturated conductance at high field value). V s is a voltage
scale factor, which gives exponential increase in conductance as V
increases. In the present study, a series of I-V characteristics at con-
stant temperature (373 K) with fitting curves to Kaiser generic
expression (equation (18)) are shown in Fig. 5a and b for all loaded
PMMA with lithium ferrite particles. With increasing ferrite parti-
cles loading the nonlinearity increases and the non-Ohmic behavior
becomes dominant. These I-V characteristics can be well fitted to
Eq. (18) and all the fitting parameters are shown in Table 4. The
high nonlinearity at higher filler loading indicate larger barrier
energies than that at lower filler loading.
From Table 4, one could observe that the low field conductance
C l shows an increase behavior with filler loading. Moreover, the m
value increases also with filler loading indicating exponential
increase in C with increasing filler loading. (m = (0.2 ! 0:79Þ:
Meanwhile, the voltage scaling parameters V s also decrease upon
filler loading above 5% weight percent reflecting the higher change
in nonlinearity of I-V characteristics above 5% filler loading.
To test the applicability of Kaiser Equation at low field region, so
log-linear plots are adopted instead of linear-linear plots, which
are shown in Fig. 6 separately. Deviations between the I-V data
and fitting curve were detected for all samples at low field. This
deviation could be possibly due to the electron–electron interac-
tion (EEI) which are not taken into account in Kaiser Equation (as
suggested by Yin et al. [55]) or in FIT model.
Fig. 6. The corresponding log-linear plots of (Theoretical and Experimental) I-V
curves of LiFe5O8 loaded PMMA with fitting curves of equation (18) at 373 K.
4.7.3. Filler dependence
Composite materials reinforced by particles possesses perma-
nent magnetic dipoles like Nd-Fe based materials are of great inter-
est due to their applications, such as hard disc components,
electrical appliances, and for automobile industry [56]. Polymer
magnetic nano-composite materials are used in many engineering
applications like electromagnetic interference shielding, sensor
technology [57], superconductors [58] etc.
Among ferrite materials, lithium ferrite (LiFe5O8) is a well inves-
tigated material and is known for its multiferroic properties. These
nano-fillers need to be embedded in the PMMA polymer matrix
with different loading in order to make this polymer suitable for
various applications. The present sub-section deals with the effect
of lithium ferrite loading on the electrical conductivity of PMMA
polymer matrix.

Fig. 5. (a and b) The linear–linear plots of I-V characteristics at constant temperature (373 K) with fitting curves to Kaiser generic expression.

Table 4
The fitting parameter C l ; m and V s of PMMA loading by LiFe5O8 of different filler volume fraction.

Fitting parameters Volume fraction of filler

0 0.00615 0.0182 0.0283 0.0852 0.134
C l (ns) 0.5 0.2 3.5 4.5 9 15
M 0.2 0.42 0.6 0.7 0.75 0.79
V s (V) 600 600 550 500 400 270
 G.M. Nasr et al. / Egyptian Journal of Petroleum 28 (2019) 361–369 367

Table 5
Electrical conductivity of PMMA nano-composites with increasing filler (lithium ferrite) volume fraction at T = 373 K

LiFe5O8 content% 0 0.00615 0.0182 0.0283 0.0852 0.134

1 1
R (X cm ) 7.419 E815 9.71E14 1.039E13 1.33E13 1.74E12 4.58E12

The observed variation of the electrical conductivity of PMMA Table 6

nano-composites with increasing lithium ferrite content is pre- The different (PTC) for the matrix and the nano-composites PMMA/LiFe5O8 at
sented in Table 5 at T = 373 K. With increasing lithium ferrite con- different filler volume fraction.
tent in the PMMA matrix, the electrical conductivity increases. Filler contents PTC (K1) (1st) PTC (K1) (2nd) PTC (K1) (3rd)
Electrical conductivity of PMMA is 10-15 (X1 cm -1). Nano- region of temp. region of temp. region of temp.
composites with filler fraction below 5 wt% present a very low con- (303–333 K) (318–363 K) (318–373 K)
ductivity close to neat PMMA. When filler fraction is above 5 wt% 0 7.16E3 – 4.4E-3
nano-composites exhibit a relatively high electrical conductivity 0.00615 0.023 0.057 0.25
(r = 4.5 * 10-12 (X1 cm-1)) but the samples still in the insulator 0.0182 0.016 0.071 0.02
0.0283 5.88E3 0.0589 0.1176
region. The conductivity increases by three order of magnitude 0.0852 0.18 – 0.092
after the percolation threshold (5 wt%). Although the nano- 0.134 0.086 0.1653 0.078
composites don’t change from insulator to conductor at 5 wt%,
but let us suppose that in the lowering filler addition (correspond-
ing to very low conductivity), there was a percolation threshold  
1 dr
which separate two region; the first one is the dispersed region ðPTC Þ ¼ ð20Þ
r dT
and the other one is the attached region (in which filler particles
begin to be close to each other). By the above assumption we try The intensity of the (PTC) effects of PMMA/LiFe5O8 composite is
to test the validity of power law model proposed by Stauffer [59]. different for different LiFe5O8 contents. Owning to the difference in
thermal expansion between the filler and the polymer matrix, the
r ¼ ro ðu  uc Þt ð19Þ composite structure is modified upon heating and this results in an
Where ro is a constant, uis the filler volume fraction, uc is the interruption of the electrical path (which in turn the PTC phe-
filler fraction at percolation threshold and t is the critical exponent nomenon is observed) [61]. To explain the different intensities of
related to the dimensionality d of the system. Cortez et al. [60] PTC detected for PMMA loaded with LiFe5O8 particles, one may
found that for d = 2, t varies from 1.1 to 1.3, and for d = 3, t is about consider that, at high filler loading the filler particles are very close
1.6! 2. The experimental data calculated for the percolation to each other, and it’s easy to form new conductive paths when the
threshold and the critical exponent for our samples are uc ¼ 0:04 interruption of paths take place upon heating. But at low filler
and t = 1.22 respectively. According to literature [60], one may con- loading the distance between filler particles is relatively large
clude that d = 2 for our system. and the possibility of forming new paths is relatively low.

4.7.4. Temperature dependence 4.8. Vibrating sample magnetometer measurements (VSM):

The temperature dependence of the bulk conductivity of the
above nano-composites is shown in Fig. 7. The electrical conductiv-
ity is almost temperature – insensitive from room temperature up
to 373 K for unloaded PMMA sample. For loaded PMMA matrix
with different ferrite contents the Positive temperature coefficient
of conductivity (PTC) is observed. The (PTC) can be tabulated in
Table 6 for the nano-composites with different filler contents (0,
1, 3, 5, 15 and 25%).
It is generally common for the soft spinel materials to have low
anisotropy, (K) (which results in a small coercivity, Hc ) with a sat-
uration magnetization at low applied magnetic field [62]. The mag-
netic properties of the PMMA/LiFe5O8 nano-composites are
displayed in Fig. 8.
The obtained magnetic parameters, like the saturation magneti-
zation (M s ), remnant magnetization (M r ) and coercive field (Hc ) are
tabulated in Table 7 with addition of magnetic parameters of pure
LiFe5O8.
The anisotropy constant (K) and magneton number (nB ) can be
determined by the equations [63,64]:

Hc M s
K¼ ð21Þ
0:96

Fig. 7. Shows the temperature dependence of the bulk conductivity of the nano-
composites PMMA/LiFe5O8 at different filler contents (1, 3, 5, 15 and 25%) and pure
PMMA matrix at constant voltage equal to 500 V.
Mw Ms
nB ¼ ð22Þ
5585
where Mw isthe molecular weight of the composition (LiFe5O8), Ms is
the saturation magnetization in Oerasted and (5585) is a magnetic
factor.
It is noticed from this table that both M s and M r increases with
increasing LiFe5O8 loading in the polymer matrix.
The calculated saturation magnetization M s increases from
(2.58) to (10.047) emu/g with increasing LiFe5O8 from (5% to
25%) as shown in Table 8. Meanwhile, the coercive field increase
upon ferrite loading. An empirical formula suggested by El-shater
et al. [62] to calculate the saturation magnetization of a mixture
of hard and soft ferrite. We try to test this formula here concerning
368 G.M. Nasr et al. / Egyptian Journal of Petroleum 28 (2019) 361–369

Fig. 8. The relation between the magnetic field (H) and the magnetization of the pure LiFe5O8 (inset) and composites PMMA/ LiFe5O8 at different filler contents (1%, 3%, 5%,
15% and 25%) at room temperature 300 K.

Table 7
shows magnetic parameters, like the saturation magnetization (M s ), remnant magnetization (M r ), coercive field (Hc ), anisotropy constant, K, and magneton numbernB

Content of (lithium Ferrite) M s (emu/g) M r (emu/g) Hc (Oe) K (Oe.emu/g) nB (Oe.gm)

0.00615 0.513 8.10E02 173.3 92.62 0.019
0.0182 1.45 0.22 175.8 265.47 0.053
0.0283 2.58 0.43 190.3 511.38 0.095
0.0852 6.16 1.06 190.9 1224.62 0.227
0.134 10.05 1.78 199.7 2090.71 0.371
Pure (LiFe5O8) 53.38 8.38 176.2 9798 1.968

Table 8
The values of the observed saturation magnetizationM s calculated saturation magnetization M s of the composites PMMA/LiFe5O8 with different filler contents (1, 3, 5, 15, and
25%) assumed that 1% is a hard phase:

Filler content 0.00615 (hard phase) 0.0182 0.0283 0.0852 0.134

CalculatedðM s Þ 0.513 1.56 2.6 7.86 13.1
ObservedðMs Þ 0.513 1.45 2.58 6.16 10.05

our data as a soft ferrite phase in a hard polymer. By considering
the PMMA matrix loaded with 1% ferrite as a hard phase with
M s;h = 0.52 emu/g:
M s ¼ M s;h ð1  uc Þ þ ðM s;s uc
where Ms;h here is the saturation magnetization of the hard phase,
Ms;s is the saturation magnetization of the soft magnetic phase and
uc is the weight fraction of the soft phase. The calculated values of
Ms (according to Eq. (23)) is represented in Table 8.
One could observe a good fitting between the calculated and the
measured values indicating the applicability of this empirical
formula.
The nonlinearity of the I-V characteristics is discussed on the bases
of Kaiser et al model which explains clearly our data. XRD studies
suggest a semi crystalline structure of filled PMMA sample with
LiFe5O8 loading 15 vol%. Moreover, increasing the LiFe5O8 load-
ð23Þ ing from 5 to 25 vol% resulted in an increase in thermal stability
and in the degradation temperature of the resultant PMMA nano-
composites. Finally, the saturation magnetization increases by
LiFe5O8 loading and achieves the value of 10.02 emu/g for PMMA
loaded with 25 vol%. A proposed formula was suggested to calcu-
late the saturation magnetization of hard phase (polymer) and soft
phase (ferrite phase), which predict well the experimental data.

References
5. Conclusions
PMMA/LiFe5O8 nano-composites were fabricated by solution
process. Both AC and DC measurement techniques were used to
study the electrical properties of the prepared samples. Both the
electrical conductivity and dielectric constant increase at a partic-
ular concentration above 5 vol%. I-V characteristics indicate a sig-
nificant increase in current with an increase in LiFe5O8 loading.
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