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Novel hybrid nanocomposites based on polyvinyl alcohol/graphene/magnetite

nanoparticles for high electromagnetic shielding performance

Ahmed A. Khodiri, Magdy Y. Al-Ashry, Ahmed G. El-Shamy

PII: S0925-8388(20)32794-8
DOI: https://doi.org/10.1016/j.jallcom.2020.156430
Reference: JALCOM 156430

To appear in: Journal of Alloys and Compounds

Received Date: 18 May 2020

Revised Date: 12 July 2020
Accepted Date: 15 July 2020

Please cite this article as: A.A. Khodiri, M.Y. Al-Ashry, A.G. El-Shamy, Novel hybrid nanocomposites
based on polyvinyl alcohol/graphene/magnetite nanoparticles for high electromagnetic
shielding performance, Journal of Alloys and Compounds (2020), doi: https://doi.org/10.1016/
j.jallcom.2020.156430.

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CRediT author statement

Ahmed A. Khodiri: Methodology, Measurements, Data Curation, Original data, Writing

M. Y. Al-Ashry: Supervision.

Ahmed G. El-Shamy: Conceptualization, Supervision, Methodology, Data analysis, Discussion,

Writing - reviewing & editing.
 45.0 a PVA/GN0.08(Fe3O4)0.02
PVA/GN0.06(Fe3O4)0.04
42.5 PVA/GN0.04(Fe3O4)0.06
40.0 PVA/GN0.02(Fe3O4)0.08

37.5
SET (dB)

35.0

32.5

30.0

27.5

25.0

22.5

20.0

8 9 10 11 12
Frequency (GHz)
Novel Hybrid Nanocomposites Based on Polyvinyl
Alcohol/Graphene/Magnetite Nanoparticles for High
Electromagnetic Shielding Performance

Ahmed A. Khodiri, Magdy. Y. Al-Ashry and Ahmed G. El-Shamy*

Physics Department, Faculty of Science, Suez Canal University, Ismailia, Egypt

Abstract

In recent times, materials with brilliant electromagnetic interference shielding (EMI)

features captured the attention thanks to their applications in military, biological, and

electronic apparatus. In this regard, hybrid polyvinyl alcohol/Graphene/Magnetite,

PVA/Gr(x)/Fe3O4(0.1-x), nanocomposites were designed for the EMI shielding

purposes. The obtained nanocomposites were characterized by various techniques like

XRD, SEM, Raman, and FTIR. XRD patterns showed that the decrease in the

crystallinity of the films with increasing the concentration of graphene (x) due to the

decrease in the hydrogen bonding inside the nanocomposite. SEM images confirm the

formation of graphene and Fe3O4 in the nano-scale with a fine dispersion in the matrix

of PVA. The magnetite Fe3O4 nanoparticles show a high impact on the magnetization

of the nanocomposites. The conductivity of the nanocomposite films increases with

increasing the concentration of graphene (x) to be 0.32, 0.46, 0.9 and 1.87 S/cm for

x = 0.02, 0.04, 0.06 and 0.08 wt.%, respectively. The EMI shielding properties of the

nanocomposite were performed in the X-band. The PVA/Gr/ Fe3O4 nanocomposites

display brilliant shielding effectiveness (SET) of 40.7 dB at 8 GHz with a very small

amount of graphene x = 0.08 wt.%, thanks to the synergetic effect of both graphene

and magnetite nanoparticles and highest electrical conductivity of the nanocomposite.

1
The main mechanism of shielding effectiveness is absorption. Finally, the synergetic

effect, fine dispersion of nanoparticles, high magnetization, and high electrical

conductivity are playing together to give this nanocomposite the advantage to be an

excellent EMI shielding material.

Keywords; PVA; Graphene nanoparticles; Iron oxide nanoparticles, EMI shielding

effectiveness; Electrical conductivity, Magnetization

*Corresponding author; Ahmed .G. El-Shamy

Tel:+201091674268
Fax: +20 064 3230416
E-mail: agabedelazim@yahoo.com

1- Introduction

The disturbance instigated by electromagnetic (EM) radiations generated by cellular

and electronic instruments like communication antennas is called the Electromagnetic

interference (EMI) [1]. The shielding mechanism from EM fields is essential for

decreasing interference from other instruments and breakdown. Interference from

microwave and radio frequencies may disturb the sensitivity of the electric apparatus

[2]. Exposure for a long time to EM radiations may cause some dangerous problems

to human health [3]. The surroundings have displayed unexpected altitude of

electromagnetic radiations, generally radio frequencies, thanks to the prosperity of

communication devices in places like health care facilities [4].

By increasing the number of apparatus that create electromagnetic radiations, it is

important to realize the EM compatibility between equipment to ensure the proper

functioning of vital life-saving systems and to ensure the safety of equipment

operators [5]. High-power EM radio frequencies are omnipresent in various working

environments, as they are widely used in such processes as dielectric welding,

industrial microwave, wireless communication, and portable devices using high-

2
power transmitters and receivers [6]. Operation of the broadcasting station for

Radio/TV signal transmitting and radar systems conjointly contribute to an oversized

quantity of electromagnetic radiations [7]. Generally, two approaches have been used

to inhibit and block the electromagnetic radiations. First, cancel the electrical field of

the electromagnetic radiations by increasing the conductivity of the shielding

materials. Second, the magnetic shielding materials have been used to cancel the

magnetic field of the electromagnetic radiations.

Electromagnetic interference was linked to a large number of materials, containing

metals, nonconducting, and/or conducting polymers and their blends [8], carbons and

their composites and/or alloys [9]. The traditional materials of EMI shielding were

practically depending on metal matrix, which was costly and heavy. As an

unconventional, nanocomposites based polymeric materials have already occupied an

essential position according to several features, high efficacy, flexibility, high

processability, and their corrosion resistance [10]. PVA polymer is considered as one

of the most interesting polymers, due to its durability, easy fabrication, availability,

and its high dielectric features and other properties [11]. On the other hand, a typical

procedure of increasing the effectiveness of the shielding materials is to integrate

dopants with high electrical conductivity in the polymer template to improve its

permeability and conductivity [12]. Among all various conductive fillers, carbon

materials such as graphite, carbon black (CB), graphene oxide (GO), carbon

nanotubes (CNTs), carbon quantum dots (CQDs) and others have been recommended

[13]. However, graphite and CB are easier to coalesce due to their higher percolation

thresholds. Alternatively, graphene and CNTs have low percolation thresholds, but

they are expensive and facing difficulties in handling and their large scale production

[14]. In fact, the shielding effectiveness (SE) of the shields depends on many factors

3
like permeability, permittivity, conductivity, and thickness of the shields [15].

However, the improving of (SE) of the shields can be achieved by enhancing

permeability and permittivity with excluding the conductivity. Many schemes have

been applied to decorate graphene as signs of progress to increase their attenuation

features against microwaves by adjusting their permittivity for example, BaTiO3 [16],

Fe3O4 [17] and others [18-20]. Among all of them, Fe3O4 nanofiller has been

extensively studied as promising materials for absorbing microwave radiations thanks

to their adequate magnetic behavior, less toxic, largely compatible, and high spin

polarization at ambient temperature [19]. Moreover, Fe3O4 nanoparticles display the

skin-depth effect and their low conductivity lets the EM radiations pass in effectively

[20]. Although the increase in the number of works to improve the shielding

properties of the polymer nanocomposite materials, the work is still open in this field

due to the shortcomings that these materials facing it. These shortcomings represent in

the appearing of the agglomeration and aggregation problems of graphene which

leads to effect on the structure of the nanocomposite and block its use in applications,

and many other problems [21].

Thus, in this work, we present nanocomposite materials based on PVA polymer

embedding with both graphene and Fe3O4 nanoparticles (Scheme 1). The PVA

polymer has been selected in this work due to its dielectric properties and

mechanically flexible behaviors [22], which allow this polymer to insert into large

production applications. The graphene has been chosen thanks to its higher

conductivity. The magnetite Fe3O4 nanoparticle was selected in this work thanks to its

magnetization function, to increase the electromagnetic shielding function. The

preparation of the nanocomposite PVA/Gr(x)/Fe3O4(0.1-x) films was successfully

done by casting technique with high homogeneity and excellent distribution, where

4
(x) is the concentration of graphene. It was found that, the crystallinity of the

nanocomposites decreased with increasing the concentration of graphene (x), this is

due to the decrease in the hydrogen bonding. At higher graphene concentration

x = 0.08 wt.%, the high electrical conductivity (1.87 S/cm) and lower magnetization

(1.89×10-3 emu/g) were recorded. Also, the highest EM shielding effectiveness SET

(40.7 dB) was obtained at this concentration. The higher magnetization

(Ms = 45.85×10-3 emu/g) of the nanocomposite was obtained at x = 0.02 wt.%,

however, this nanocomposite records the lowest SET value. This is maybe due to the

high dielectric behavior of the magnetite nanoparticles. The contribution of the

shielding by absorption is larger than by the reflection of PVA/Gr/Fe3O4

nanocomposite. Finally, the fine dispersion, high magnetization, and high electrical

conductivity are playing together to give this nanocomposite the advantage in many

practical applications such as EMI shielding materials and bio-devices.

2- Experimental details.
2.1- Materials
Polyvinyl Alcohol (Mw= 115000 g/mol, purity 99.99%), Graphite powder (99.98%),

Iron (II) chloride FeCl2.4H2O (Mw= 126.75 g/mol, purity 99.99%), Iron (III) chloride

FeCl3.6H2O (Mw= 270.30 g/mol, purity 99.99%), Potassium permanganate (KMnO4,

99.99%), Sodium nitrate (NaNO3, 99.99%), Hydrogen peroxide (H2O2, 99.99%),

Hydrochloric acid (HCl, 99.99%) and Sulfuric acid (H2SO4, 99.99%) were obtained

from Loba Chem. PVT. LTD; India

2.2- Preparation of Graphene (Gr) nanoparticles

Graphene nano-filler was synthesized via an exfoliation process of graphite oxide.

Graphene oxide was synthesized as a result of the oxidation process of purified

natural graphite according to the modified Hummers method, as reported elsewhere

5
[23]. In this method, an appropriate amount of (graphite powder + NaNO3) was

dissolved in 70 ml of H2SO4. The temperature of the reaction was controlled below

20ᴼC. Then, 9 g of KMnO4 was slowly added to the above solution over 1 h and then

followed by stirring for another 1 h, and then the mixture is stirred for 30 min at

35 ± 3ᴼC. After cooling the mixture to room temperature, 150 ml of deionized water

was slowly added to the mixture, and this is accompanied by raising the temperature,

to obtain a yellowish suspension. After that, the mixture had additionally treated with

400 ml of deionized water and 30 ml of 5% Hydrogen peroxide solution, to remove

the remaining permanganate ions. To remove the sulfate ions, the solution was filtered

and washed with a 10% HCl aqueous solution [24]. The filtration powder was

exfoliated to obtain the graphene powder as reported in the literature [25].

2.3- Preparation of Fe3O4 nanoparticles

Magnetite Fe3O4 nanoparticles were synthesized in an aqueous solution via

co-precipitation method, as reported elsewhere [26,27]. In this method, appropriate

amount of (FeCl3.6H2O + FeCl2.4H2O) was dissolved in 25 ml of 0.40 M HCl. After

the complete dissolving, 250 ml of 1.5M NaOH solution was added drop-wise to the

above solution under vigorous stirring for 30 min. After a brownish-black (Fe3O4)

precipitates were formed, the solution was centrifuged at 4000 rpm, then washed with

water and dried in the oven for 6 h.

2.4- Preparation of PVA/Gr/Fe3O4 nanocomposite films

The casting technique was used to prepare the PVA/Gr/Fe3O4 nanocomposite films

[1,3,11,13,21,22,28-34] as a follow: 2 g of PVA powder was dissolved in distilled

water for 30 min at 60-70 ᴼC until a clear solution was obtained. Once the PVA

solution became viscous, the solution of Gr(x)/Fe3O4(0.1-x) nanoparticles was added

drop/second to the PVA solution and stirrer to another 60 min. After that, the obtained

6
solution was cast in a glass dish and left to dry in atmospheric conditions. The

thickness of the films was determined by using a digital caliper and found to be

200 μm.

2.5. Instruments and Method

XRD patterns of the obtained samples were studied by using (Malvern Panalytical

Empyrean X-ray Diffractometer, United Kingdom), with Cu Kα radiation (λ= 0.15406 nm)

and scanning range 2θ = 4o to 80o. The d-spacing and the crystallite size of the

samples were determined from the equation [1,3,11,13,21,22,28-34]:

2d sin θ = n λ (1)

D =kλ (2)
β cos θ

Where D is the crystallite size, k is a factor related to the crystallite shape, λ is the

wavelength (0.154 nm for Cu Kα), β is the Full width at half maximum (FWHM in

radian) and θ is the peak position (2θ in degree). SEM (Quanta FEG-250, LMA,

Dublin, Ireland) was used to study the surface morphology of the PVA/Gr/Fe3O4

films. Raman spectroscopy (model alpha 300R/AS from witechulm, Germany) was

applied for graphene, Gr/Fe3O4 nanoparticles, and PVA/Gr/Fe3O4 films to detect the

vibrational modes and study their structures. Fourier Transform Infrared (FTIR)

spectrophotometer, Model: Nicolet DTGS TEC detector, was used to identify the

chemical bonds and the compositions of the nanocomposite films in the wavenumber

range from 4000 to 400 cm-1. The conductivity of the films was measured by using

(Keithley 6517B) electrometer by coating both sides of the film with silver paste. The

equation σ = d RA (S/cm) was applied to determine the conductivity, where (A) is the

area of electrodes, (d) is the thickness of the film and R is the resistance of the film.

The magnetic properties of the samples were investigated using a vibrating sample

7
magnetometer VSM 7400-S series (Lake Shore Cryotronics, Ohio, USA) at room

temperature. The electromagnetic interference EMI shielding parameters of the

samples were tested by VNA (Agilent-N9918A, Keysight, USA) using the waveguide

method in the X-band frequency (8 –12 GHz) range according to ASTM D5568-08.

The dimension of the samples was 30 mm × 30 mm.

The total shielding effectiveness SET can be calculated from equation (3). In fact, SET

equals the summation of shielding effectiveness due to reflection SER, shielding

effectiveness due to absorption SEA, and shielding effectiveness due to multiple

internal reflections (SEM) [1,3].

SET (dB) = SER + SE A + SEM (3)

In fact, when SET ≥15 dB, the contribution due to multiple internal reflections (SEM)

is insignificant and becomes negligible. This is attributed to in the case of the thick

shielding materials like in our case; the penetrated EM waves inside the film suffer

from multiple reflection processes between the two boundaries (surfaces) of the film

producing a high absorption of EM waves (SEA). The multiple reflection process

repeats more than one time ‘’thousands of times’’ until the amplitude of the EM

reflected waves become very small and can be neglected the shielding effectiveness

due to multiple reflections (SEM ≈ 0). Practically, in this case/state the SEA is equal or

larger than 10 dB and the total shielding effectiveness due to reflection and absorption

SET ≥15 dB. Moreover, the SEM can be described from the following equation.

 -2d
δ   -SEA 10 
SE M =20 log 1-e  =20 log  1-10  (4)
   

Where (d) is the thickness of the sample and (δ) is the skin depth and defined as the

thickness below the outer surface at which the incident field is attenuated to 1/e of its

initial value. From the above equation, the SEM depends on (d) and is closely related

8
to absorption. Based on this equation when the thickness of the shielding materials is

greater than the penetration depth (δ), the shielding effectiveness due to multiple

reflections (SEM) can be neglected (more discussion see Supplementary Materials).

According to the above statement, the total shielding effectiveness SET can be stated

as,

SE T =SE R +SE A
(5)

Therefore, the shielding effectiveness due to reflection (SER), absorption (SEA) and

the total shielding effectiveness (SET) are stated from the equation [1,3];

2
R= S11
2
T= S21
1 1
SE R =10log( )=10log( 2
) (6)
1-R S11
2
1-R 1- S11
SE A =10log( )=10log( 2
) (7)
T S21

On the other hand, the dielectric constants (real part ε ' and imaginary part ε '' ) can be

determined from the S-parameters (S11 and S21) according to Nicholson-Ross-Weir

model as follows:

R (1 −T 2
) , and S T (1 − R 2 )
S 11 = = (8)
(1 − R T
2 2
) 21
(1 − R T )
2 2

Where R is the reflection coefficient and T is the transmission coefficient. In fact, the

reflection coefficient (R) can be deduced as:

R = X ± X 2 −1 (9)

Where |R| < 1 is required for finding the correct root (X) in terms of the

S-parameters

9
 S 112 − S 212 + 1
X = (10)
2S 11
The transmission coefficient (T) can be written as:
S + S 21 − R
T = 11 (11)
1 − ( S 11 + S 21 ) R

The relative permeability is given as:

1+ R
µr = (12)
1 1
Λ (1 − R ) −
λo2 λc2

2
1  ε r µr 1   1  1 
= 2 − 2 = ln    (13)
Λ  λo
2
λc   2π L  T  

Where λo is free space wavelength and λc is the cut-off wavelength and L is a material

length. The relative permittivity can be defined as:

λo2  1  1 
2
1
εr =  2 − ln     (14)

µ r  λc  2π L  T   

Eqs. (13) and (14) have an infinite number of roots since the imaginary part of the

term ln 1
T ( ) is equal to j (θ + 2π n ) , where n = 0, ± 1, ± 2,... , is the integer of

( L / λ ) . Then ( n ) can be determined by estimating from

g λg using initial guesses

values of ε r* and µ r* for the sample. From Eq. (13), we have

2
1  γ  2π λ 
= j  , Where γ = j ε r* µr* −  o  (15)
Λ  2π  λo  λc 

1 1
= (16)
Λ λg

Where ε = ε ' − jε ''

The skin depth ( δ ) was calculated from the equation

10
δ= 1 (17)
π f µ rσ

Where ε r is the relative permittivity, µr is the relative permeability, ε r* is the initial

guess permittivity, µ r* is the initial guess permeability, λg is the wavelength in the

sample, γ is the propagation constant of the material, and σ is the conductivity of the

sample. By equating the Eqs (15 and 16), λg can be determined and hence the ( n )

value. Once the ( n ) value is determined, the permittivity ε r can be determined.

3- Results and discussion.

3.1. Characterization of the PVA/Gr/Fe3O4 nanocomposites.

In fact, the casting technique has been used in this study to prepare polymeric

nanocomposite films. Indeed, there is an interaction that takes place between the

nanofillers and the matrix of PVA when the graphene and magnetite nanoparticles

were embedded into the PVA matrix. Significantly, the hydrogen bonding interaction

produces between the nanofillers and (OH) groups of PVA, which may be reflected in

the crystallinity, structure, morphology, and properties of the nanocomposites. To

study the effect of both graphene and magnetite nanoparticles and their synergetic

effect on the structure and properties of the nanocomposite, the XRD patterns of the

nanocomposite were carried out (Fig 1). As seen, Fig. 1a displays the X-ray pattern of

the graphene oxide. There is a sharp peak at 2θ=10.7o, this peak is attributed to the

(hkl) plane (001) of the graphene oxide. The distance between graphene oxide layers

was calculated and found to be (0.83 nm). This value matches the value reported in

the literature [35], which means the graphene oxide has been successfully prepared by

the Hummer method. The inset of Fig 1a shows the XRD pattern of the graphene

nanoparticles. A sharp peak was observed at 2θ=26.5o for the hkl plane (002) of the

11
graphene nanoparticles. Moreover, the distance between the graphene layers was

found to be (0.34 nm). This value matches the value in literature [36,37].

Fig.1b shows the XRD pattern of Fe3O4 powder. There are eight XRD patterns were

detected at 2θ= 18.3o, 30.1o, 35.5o, 43.3o, 53.5o, 57.2o, 62.7o and 74.31o for the hkl

planes (111), (220), (311), (400), (422), (511), (440) and (533) for the face-centered

cubic structure (FCC) of the Fe3O4 nanoparticles according to JCPDS (space group

Fd3m (227), JCPDS #89-4319) [38]. The crystallite size of Fe3O4 particles was

determined for the plane (311) and it was found to be 20 nm. In fact, similar results

were observed in the literature [39].

On the other hand, the XRD patterns of the nanocomposite have been done to study

the synergetic effect of both graphene and magnetite nanoparticles on the structure of

nanocomposites. Fig. 1c shows the XRD patterns of the nanocomposite films with

changing the concentration of graphene (x). As seen, the pure PVA film has a peak at

2θ= 19.5o, this peak is attributed to the (101) plane of the crystalline part of the semi-

crystalline PVA polymer (Fig. 1d) [40]. Besides this peak, another peak appeared at

2θ= 6.5o when embedding the graphene into the PVA matrix (Fig.1c). The appearance

of this peak is attributed to the formation of scattering planes due to the strong

interaction between PVA chains and graphene. This peak was appeared in many

previous works [41]. The intensity of the peak at 2θ= 19.5o decreases with increasing

the concentration of graphene (x) in the matrix of PVA, which means decreasing the

crystallinity (increasing the amorphous phase) of the nanocomposite. The crystallinity

was determined from the integrated area under the crystalline regions divided by the

integrated areas of both crystalline and amorphous regions [1,3,11,13,21,22,28-34].

The crystallinity was found to be 40.21, 39.01, 37.89, 37.02 and 36.10 % for x= 0,

0.02, 0.04, 0.06 and 0.08 wt.%, respectively. The reason behind the decrease in the

12
crystallinity is attributed to the decrease in the hydrogen bonding (intra/inter types)

inside the nanocomposite. This is may be due to the consuming of the (-OH groups)

which are responsible for the crystallinity of the PVA polymer during the interaction

between PVA and the functional groups of the graphene [42]. The increasing of the

amorphous phase of the nanocomposites leads to increasing the segment mobility of

the polymer, improving the conductivity of the films [43,44], and hence improving

the shielding behavior. These results agree with the results that are reported before

[45].

SEM images of the prepared samples were performed (Fig 2). Fig. 2a shows the SEM

image of the graphene. As seen, the structure of graphene consists of a similar

intertwined layered structure. Each particle of graphene contains several sheets with

an average sheet diameter of 4 mm. Fig.2b shows the SEM images of the Gr/Fe3O4

nanoparticles. It is clear that the Fe3O4 nanoparticles have an average particle size

12 nm, confirming the presence of Fe3O4 in nano-scale with spherical shape and

without any agglomeration. In fact, this type of structure/morphology of both

graphene and magnetite is very important, which helps to improve the EM absorbing

features of different shields, as they serve as centers of EM waves attenuation or trap

centers of electric /magnetic field producing an electric/magnetic loss. Fig. 2c-f shows

the SEM images of the (PVA/Gr/Fe3O4) film surfaces at different concentration of

graphene (x). The SEM images were performed to study the morphology of the film

surface. As shown, both the graphene and the magnetite nanoparticles are well

dispersed in the matrix of the PVA. The high degree of the homogeneity and fine

distribution of both fillers were obtained (Fig. 2c,d). Moreover, at the sample with

x= 0.02 wt.% of graphene, there is a high degree of agglomeration and aggregation of

the magnetite (Fe3O4) nanoparticles in the films; this is attributed to the magnetic

13
(magnetization) function of the (Fe3O4) nanoparticles. This magnetic function leads to

agglomerate the (Fe3O4) nanoparticles during the evaporation of the solvent.

However, with increasing the concentration of (x) in the samples, which means

decreasing the Fe3O4 concentration, the agglomeration of Fe3O4 was reduced due to

the reduction in their concentration (Fig. 2e,f). Increasing the concentration of (x)

leads to producing a high packing density of the graphene in the sample; therefore,

improving the particle-to-particle connection function and hence increasing the aspect

ratio parameter [46]. This reflects increasing the electrical conductivity of the

nanocomposite and high EMI shielding [47].

Fig. 3a shows the FTIR spectra of the nanocomposite PVA/Gr/Fe3O4 films with

different concentrations of graphene (x). Fig. 3a shows the characteristic peaks of the

magnetite Fe3O4 nanoparticles at around 538–573 cm−1. The broad absorption band at

3261 cm−1 is attributed to the stretching mode of hydroxyl groups (-OH) in PVA. The

intensity of this band decreases with increasing the concentration of graphene (x), this

is due to the reduction in the hydrogen H-bonding between the nanofillers and the

PVA, which is reflected in the decreasing the crystallinity. The bands at 2928 and

2865 cm−1 represent the symmetric and asymmetric C-H stretching vibrations of the

methylene (-CH2-) group. A peak at 1731 cm−1 is attributed to the C=O stretching

vibration of the PVA. Functionalized graphene displays at a peak of 1087 cm-1 for the

COOH group. The intensities of these bands decreased with increasing the

concentration of graphene (x), which confirms the strong interaction between the

graphene and PVA chains. Besides, the existence of Fe3O4 in the composite was also

detected with the appearance of peaks at around 538–573 cm−1 for Fe-O vibrations. In

General, the characterization results indicated that the PVA/Gr/Fe3O4 composite was

successfully synthesized and can be applied for further research.

14
Raman spectra of the graphene, Gr/Fe3O4 nanoparticles, and PVA/Gr/Fe3O4

nanocomposite films were performed (Fig.3b) to detect their vibrational modes and/or

structures. It is clear that the graphene has three Raman spectra at 1314.35, 1630.60,

and 2672.67 cm-1, respectively. The spectrum at ~1630.60 cm-1 is due to the G-band,

which is coming from the E2g of the hybridization of carbon (sp2 type) and the

spectrum at ~1314.35 cm-1 is due to the D-band, which is coming from the vibrations

of the sp3 carbon atom of defects and disordered graphite. The 2D peak was detected

at 2672.67 cm-1 due to double Raman scattering near the k point of the Brillouin zone

[48]. The intensity of these spectra is decreased when the magnetite decorated

graphene; this is maybe due to the decoration of graphene with magnetite, where the

Fe3O4 nanoparticles fill the defects on the surface of graphene. Indeed, the ratio

(I2D/IG) is directly related to the number of graphene layers [49,50]. In fact, when the

ratio I2D/IG was about ≈ 2–3, this refers to monolayer graphene, when the ratio was

2 > I2D/IG > 1 this refers to bilayer graphene and multilayer graphene was found when

I2D/IG < 1. The ratio (I2D/IG) was determined for graphene and it was found to be

(0.35), which indicates that the obtained graphene in our work has multilayers

structure [45,46]. In fact, the (ID/IG) ratio numerically presents the number of defects

in graphene, the (ID/IG) ratio is determined and was found to be (0.56), and this value

increases for Gr/Fe3O4 and PVA/Gr/Fe3O4 composite. However, this value is very

small as compared to other values reported before [53]. This refers that a small

number of defects on the surface of graphene and small amount of functional groups

are present [54,55]. These results agree with the FTIR spectra reported in the above

section. This behavior leads to improve the carrier mobility of the Gr/Fe3O4

nanoparticles and hence improving the EMI shielding performance.

15
3.2. Magnetic properties of the nanocomposite films

The hysteresis loops of the nanocomposites were measured to study the impact of the

magnetite (Fe3O4) nanoparticles on the magnetic behavior of the nanocomposite films

(Fig.4). In fact, Fig.4 presents the hysteresis loops of the PVA/Gr/Fe3O4

nanocomposite films at room temperature (300 K). The magnetic parameters (Ms, Mr,

and Hc) are tabulated in Table 1. From Fig.4, the S-like shape of the hysteresis loop

was obtained for the PVA/Gr/Fe3O4 nanocomposite. The saturation magnetization

(Ms) of the PVA/Gr/Fe3O4 nanocomposite was found 1.89×10-3 and 45.85×10-3 emu

g−1 for the graphene concentration x= 0.08 and 0.02 wt.%, respectively. As seen, the

value of Ms for the nanocomposite at x=0.02 is higher than that of x= 0.08, this is

maybe due to the graphene at x=0.08 has more (OH) groups, which slightly weakens

the magnetic performance. Table 1 shows with decreasing the concentration of (x),

increasing the Fe3O4 concentration, the corresponding maximum saturation

magnetization increased continuously, which demonstrates the magnetization function

of the composites at room temperature. Increasing the ratio of Fe3O4 nanoparticles

against graphene shows an increase in the saturation magnetization (Ms) with small

coercivity (Hc). This is produced when a large concentration of non-magnetic material

(graphene) introduced in the nanocomposite, which decreases the magnetic

parameters. But, increasing the concentration of Fe3O4 nanofillers in the matrix boosts

the magnetization in the graphene. This allows the graphene to match its dielectric

parameters with magnetic parameters so that the impedance-matching characteristics

of the graphene are increased, producing a high EMI shielding material.

3.3. Electrical conductivity of the nanocomposite films

The electrical conductivity of the PVA/Gr/Fe3O4 nanocomposites was measured as a

function of graphene (x) and depicted in (Fig 5). The electrical conductivity of the

16
nanocomposite films increases dramatically with increasing the concentration of

graphene (x). Even at a low concentration of (x), the conductivity of the

nanocomposite improved from 6.9 ×10-7 S/cm for pure PVA to 0.32 S/cm at

x= 0.02 wt.%. The conductivity increased with increasing the concentration of

graphene (x) and it was found to be 0.46, 0.90 and 1.87 S/cm for the x= 0.04, 0.06 and

0.08 wt.%, respectively. The reason behind increasing the conductivity is attributed to

the superior electrical conductivity of graphene and its high aspect ratio. The

graphene-based sheet structure leads to make a huge conducting network in the

nanocomposite which creates a decrease in the film resistivity (ρ). These results agree

with the SEM results. Similar behavior was observed in Ref. [45]. In fact, the

nanocomposite films with high conductivity have benefits in electromagnetic

shielding materials.

3.4. EMI shielding Properties

Fig.6a shows the total shielding effectiveness (SET) of the nanocomposite as a

function of graphene (x) in the X-band. It is clear that the value of SET is increased by

increasing the concentration of (x) in the nanocomposite. This is due to the increase in

graphene (x) concentration, which improves the particle-to-particle connection

behavior by increasing the aggregation of graphene nanosheets in the polymer

network and this gives superior SET of nanocomposites as proven by SEM

micrographs in (Fig 2a,b). The total shielding effectiveness SET value of the

nanocomposite was measured to be 20.68 dB at x = 0.02 wt.% at 8 GHz. However,

the values of SET were measured and found to be 27.38, 31.23, and 40.7 dB at 8 GHz

for x= 0.04, 0.06, and 0.08 wt.%, respectively. That is can be said; the increase in

graphene leads to improving the EM shielding features of nanocomposites. Moreover,

the growth of graphene produces more continuous conductive paths and producing a

17
higher density of electrons or holes (mobile charge carriers) in the nanocomposites,

which interacts with an incident EM field and hence increasing the SET of

nanocomposites [1,3,56,57]. These results indicate that the PVA/Gr/Fe3O4

nanocomposites can be good shielding materials in industrial commercial

applications.

The EM shielding mechanism can be illustrated in (Fig. 6b). When the EM wave falls

on the film, a portion of the wave is reflected just when reached to the film surface

and the residual portion penetrates the film (Fig. 6b). A portion of the penetrated wave

was absorbed by graphene, Fe3O4, and PVA segments. The penetrating waves reach to

the Gr/Fe3O4 nanoparticles and divided into the absorbed part, transmitted part, and

the other part will be reflected by Gr/Fe3O4 nanoparticles that located close to the film

surface, producing an internal reflection between the Gr/Fe3O4 and the internal

surface of the film. The internal reflected waves will be reflected and absorbed over

and over by the Gr/Fe3O4 in the films, and finally, vanish (this explains why multiple

reflected SEM is negligible). This operation can be repeated again and again inside the

film due to thousands of the nanoparticles. At the end, a very small portion of waves

can leave the film.

The SEA and SER values were studied as a function of graphene (x)

(Fig 6c,d). It is clear that SEA and SER are increased by increasing the concentration

of (x) in the nanocomposite. However, the SEA values are larger than the SER values,

which mean the contribution of the shielding by absorption is larger than by the

reflection of PVA/Gr/Fe3O4 nanocomposite. The reason behind the increase in SEA

value is attributed to the increase in the crosslinking density and connectivity behavior

of the PVA/Gr/Fe3O4 nanocomposite with increasing the concentration of graphene

(x). Moreover, the larger Ohmic loss and polarization loss are the reasons behind the

18
higher absorption value with increasing the concentration of (x) [45]. Indeed, a large

number of the conductive networks and also a large number of mobile charge carriers

are produced in the nanocomposite by increasing the concentration of graphene which

can reduce the penetrating wave. In addition, the processes of multiple dipole

relaxation (electric and magnetic dipoles) at interface regions, moreover, the

dissipation effect of charge carriers in the nanocomposite were sharing in the

absorption of the microwave.

The skin depth was calculated from the (Eq. 15) and depicted in Fig 7. The reduction

in the skin depth was detected by increasing the concentration of graphene (x) in the

nanocomposite. This reduction is attributed to the large aspect ratio of graphene

nanosheets and high charge carrier concentrations at the surface. This leads to ease

interaction at the interface regions between the incident EM fields and the charge

carriers in the nanocomposite.

The dielectric constants of the nanocomposite were calculated according to

Nicholson-Ross-Weir (NRW) method [58,59] using the S-parameters (Fig. 8a,b).

Fig. 8a shows the real dielectric constant ( ε ' ) as a function of the graphene (x). The

growth of the dielectric constant was observed with increasing the concentration of

(x). The reason behind the increase in the real dielectric constant is attributed to the

growth of the free charge carrier’s concentration in the nanocomposite producing a

large EM absorption. Moreover, the growth of the interfacial polarization between the

segments of the polymer and the graphene leads to an increase in the dielectric

constant [45]. Fig 8b shows the dielectric loss ( ε ' ' ) of the nanocomposite as a function

of graphene (x). The dielectric loss was gradually increased with increasing the

concentration of (x). This is due to the increase of the conductivity of the

nanocomposite with the concentration of graphene (x), which makes a continuous

19
conductive path of graphene and increase the conductivity and hence increase the

dielectric loss according to the relation σ = 2π f ε oε '' [1,3,11,13,21,22,28-34].

The comparison between the SET of our polymeric (PVA/Gr/Fe3O4) nanocomposite

films and the previous reported non-conductive and conductive polymeric

nanocomposite films in the X-band frequency was performed in Table 2. As seen, the

(PVA/Gr/Fe3O4) materials possess (SET = 40.7 dB) value greater than the (SET) value

of other materials for instance Gr/PDMS Foam (20 dB), Gr/Fe3O4/epoxy (~17 dB),

CNWs/Gr/PDMS (36 dB), PDA-rGO Foam (26.5 dB), Gr Foam (~25.2 dB) and

Fe3O4/Gr/PDMS (32.4 dB). Moreover, the (PVA/Gr/Fe3O4) materials possess (SET)

value smaller than the (SET) value of other materials for instance CNTs/Gr/PDMS

cake (67.3 dB) and Fe3O4@rGO/NR (~43 dB). From this analogy, our nanocomposite

(PVA/Gr/Fe3O4) has some features when compared with other polymeric

nanocomposites, like its fast and easy production, its flexibility, eco-friendly,

affordable, its ease processability, usage of small amounts of raw materials and non-

toxic material. Additionally, one of the most important advantages of this

nanocomposite is obtaining high conductivity and shielding properties with a very

small amount of graphene and Fe3O4. However, our nanocomposite shows some

shortcomings such as its SE value and conductivity are still slightly lower than the

other polymeric nanocomposites. Finally, it can be suggested that increasing the

concentration of both graphene and Fe3O4 nanoparticles or doping this nanocomposite

with fillers with high electrical and magnetic properties maybe improve the SE of the

producing nanocomposite. Moreover, we can use the conducting polymer such as

poly(3,4-ethylene-dioxythiophene) PEDOT and/ or poly (styrenesulphonate) PSS

polymers and other polymers to enhance the electrical conductivity and hence,

increasing the SE of the nanocomposite.

20
4- Conclusions.

In this work, the nanocomposite (PVA/Gr/Fe3O4) films have been successfully

prepared by the casting technique for electromagnetic shielding applications. The

structure, morphology of the (PVA/Gr/Fe3O4) films and their magnetic and electrical

properties were influenced by the synergetic effect of both graphene and Fe3O4

nanoparticles. The crystallinity of the films was decreased with increasing the

concentration of graphene due to the reduction in the hydrogen bonding inside the

nanocomposites. The magnetization of the nanocomposite was decreased with

increasing the graphene thanks to the increase of the functionalized (OH) group,

which slightly weakens the magnetic performance. The conductivity of the

nanocomposite films increases with increasing the concentration of graphene (x) due

to the formation of the conductive path of graphene. The dielectric constant was

increased with increasing the concentration of graphene due to the growth of the free

charge carrier’s concentration in the nanocomposite and the growth of the interfacial

polarization between the segments of the polymer and the graphene. The

electromagnetic shielding effectiveness (SET) increased with increasing the graphene,

due to the increase in the number of continuous conductive paths and increasing the

density of electrons or holes (mobile charge carriers) in the nanocomposites. At very

small amount of graphene (x= 0.08 wt.%), the nanocomposite displays a high SET

value of 40.7 dB and high conductivity of 1.87 S/cm. The absorption of the EM wave

was the main mechanism of the shielding effectiveness properties of the

nanocomposites. Finally, it can be recommended that the (PVA/Gr/Fe3O4)

nanocomposites can be inserted commercially into many appliances like vehicular

detection, broadcasting satellites, defense tracking, radar, weather satellite, household

applications or more as a shielding material.

21
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27
Figure caption

Scheme 1, the scenario of the preparation steps of the graphene (Gr) nanoparticles, Magnetite

nanoparticles (Fe3O4), and the nanocomposite PVA/Gr/Fe3O4 films

1
a Graphene Oxide Powder
b

(311)
(001)

Fe3O4 NP Powder

(002)
Graphene
Intensity (a.u.)

Intensity (a.u.)
Intensity (a.u.)

(440)
(220)

(511)
(400)

(422)
(111)

(533)
20 30 40
ε(degree)

10 20 30 40 50 60 70 80
10 20 30 40 50 60 70 80
2θ (degree) 2θ (degree)

c
(101)
X=0.08
X=0.06
X=0.04
Pure PVA
d
X=0.02
Intensity (a.u)

Intensity (a.u)

0 10 20 30 40 50 60 70 80
0 10 20 30 40 50 60 70
2 (Degree)
2θ (degree)

Fig. 1, shows the XRD patterns of (a) graphene oxide (GO) and the inset of figure (a) shows the XRD

patterns of graphene (Gr) nanoparticles, (b) XRD patterns of magnetite Fe3O4 nanoparticles, (c) the

XRD patterns of the nanocomposite PVA/Gr/Fe3O4 films with different concentration of graphene

(x), and (d) XRD pattern of the pure PVA.

2
a b

c X=0.02 X=0.04 d

3
 e X=0.06 X=0.08 f

Fig. 2 (a) The SEM image of as prepared graphene (Gr) nanoparticles, (b) SEM image of

Gr/Fe3O4 nanoparticles. (c-f) The SEM images of the nanocomposite films at different

concentration of graphene (x), (c) x= 0.02 wt.% (d) x = 0.04 wt.% (e) x = 0.06 wt.% and (f)

x= 0.08 wt.%

4
 a b
PVA/Gr/Fe3O4
X= 0.08 Gr/Fe3O4 ID/IG = 1.04
X= 0.04
X= 0.06 Gr D
G
X= 0.02
I2D/IG = 0.12 2D

Intensity (a.u)
Transmittance (a.u.)

ID/IG = 0.83
D G
I2D/IG = 0.09
2D
G
ID/IG = 0.56

D
C=O I2D/IG = 0.35
C-H C=C 2D
OH
COOH
Fe3O4

4000 3500 3000 2500 2000 1500 1000 500 800 1200 1600 2000 2400 2800
-1
wavelength (cm ) Raman Shift (cm )
-1

Fig 3, (a) FTIR spectra of the PVA/Gr/Fe3O4 nanocomposites with different concentration of

graphene (x), (b) Raman spectra of Graphene (Gr) nanoparticles, Gr/Fe3O4 nanoparticles and the

nanocomposite PVA/Gr/Fe3O4 film

5
 0.04 X=0.08
X=0.02
Magnetization (emu/g)

0.02

0.00

-0.02

-0.04

-20000 -10000 0 10000 20000

Magnetic Field (G)

Fig. 4, shows the hysteresis loops (Magnetization versus magnetic field) of the nanocomposite

PVA/Gr/ Fe3O4 films at concentration of graphene x= 0.02 and 0.08 wt.%

6
 2.0

1.8

1.6
Conductivity (S cm )

1.4
-1

1.2

1.0

0.8

0.6

0.4

0.2

0.02 0.04 0.06 0.08

X (wt.%)

Fig. 5, shows the electrical conductivity of the nanocomposite PVA/Gr/Fe3O4 films with different

concentrations of graphene x = 0.02, 0.04, 0.06 and 0.08 wt.%

7
a b
45.0 X= 0.08
X= 0.06
42.5 X= 0.04
X= 0.02
40.0

37.5

35.0
SET (dB)

32.5

30.0

27.5

25.0

22.5

20.0

8 9 10 11 12

Frequency (GHz)

c
18

16
X= 0.08
X= 0.06
X= 0.04
X= 0.02
27.5 X= 0.08
X= 0.06
X= 0.04
X= 0.02
d
25.0
14

12
22.5
SER (dB)

SEA (dB)

10

8
20.0
6

4
17.5
2

8 9 10 11 12
8 9 10 11 12
Frequency (GHz) Frequency (GHz)

Fig.6 (a) shows the total shielding effectiveness (SET) of the nanocomposite PVA/Gr/Fe3O4

films, (b) shows the EM Shielding mechanism inside the nanocomposite films (c) SER and (d)

SEA of the nanocomposite PVA/Gr/Fe3O4 films with different concentration of graphene

x = 0.02, 0.04, 0.06 and 0.08 wt.%

8
 0.11 X= 0.08
X= 0.06
X= 0.04
0.10 X= 0.02

0.09
Skin depth (mm)

0.08

0.07

0.06

0.05

0.04

0.03
8 9 10 11 12
Frequency (GHz)

Fig. 7 shows the Skin depth of the nanocomposite PVA/Gr/Fe3O4 films with different

concentration of graphene x = 0.02, 0.04, 0.06 and 0.08 wt.%

9
 a b
10
X=0.08
18 X=0.06
X=0.04 9 X=0.08
X=0.02 X=0.06
X=0.04
16 8 X=0.02
Real dielectric constant ε'

Dielectric loss ε''

7
14

12
5

10 4

3
8

8 9 10 11 12 8 9 10 11 12
Frequency (GHz) Frequency (GHz)

Fig. 8 shows the Complex dielectric constants (a) Real dielectric constant, and (b) Dielectric loss

of the nanocomposite PVA/Gr/Fe3O4 films at different concentration of graphene x = 0.02, 0.04,

0.06 and 0.08 wt.%

10
 Table 1; The magnetic parameters of PVA/Gr(x)/Fe3O4(1-x) composites.

Magnetic Parameters PVA/Gr(0.02)/Fe3O4(0.08) PVA/Gr(0.08)/Fe3O4(0.02)

Ms (emu/g) 45.85×10-3 1.89×10-3

Hc (Oe) 10.55 12.82

Mrs (emu/g) 610.98×10-6 45.23×10-6

Table 2, Microwave shielding values of different polymeric nanocomposites

Composite Thickness Electrical Conductivity SET (dB) Frequency range Ref.

(mm) (S/cm) (GHz)
Gr/PDMS Foam ~1 2 20 8–12 [60]
CNTs/Gr/PDMS cake ~1 15.15 67.3 8.2–12.4 [61]
Fe3O4@rGO/NR ~1.8 >0.1 ~43 8.2–12.4 [62]
Gr/Fe3O4/epoxy ~2 >0.01 ~17 8–12 [63]
CNWs/Gr/PDMS ~1.6 3.4 36 8.2–12.4 [64]
PDA-rGO Foam ~0.032 0.72 26.5 8.2–12.4 [65]
Gr-Foam 0.3 3.1 ~25.2 8.2–12.4 [66]
Fe3O4/Gr/PDMS ~1 2.5 32.4 8.2–12.4 [67]
PVA/Gr/Fe3O4 0.2 1.8 40.7 8-12 This
work

PDMS = Polydimethylsiloxane, NR = Natural rubber, PDA = Ploydopamine and PVA =

Polyvinyl alcohol.

11
Highlights

The nanocomposites PVA/Gr(x)/Fe3O4(0.1-x) have been prepared via the casting

method for electromagnetic shielding.

The highest electrical conductivity of the PVA/Gr/Fe3O4 nanocomposite was

1.87 S/cm at graphene concentration x=0.08 wt.%.

The nanocomposites displayed EMI shielding effectiveness (SET) of 40.7 dB

at very small amount of graphene x= 0.08 wt.%.
Declaration Of Interest

There is no declaration of interest