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Investigation of gamma ray attenuation features of bismuth oxide nano powder

reinforced high-density polyethylene matrix composites

Alyaa H. Abdalsalam, Erdem Şakar, Kawa M. Kaky, M.H.A. Mhareb, Betul Cevi̇z
Şakar, M.I. Sayyed, Ali Gürol
PII: S0969-806X(19)30253-1
DOI: https://doi.org/10.1016/j.radphyschem.2019.108537
Reference: RPC 108537

To appear in: Radiation Physics and Chemistry

Received Date: 19 March 2019

Revised Date: 1 September 2019
Accepted Date: 18 October 2019

Please cite this article as: Abdalsalam, A.H., Şakar, E., Kaky, K.M., Mhareb, M.H.A., Cevi̇z Şakar, B.,
Sayyed, M.I., Gürol, A., Investigation of gamma ray attenuation features of bismuth oxide nano powder
reinforced high-density polyethylene matrix composites, Radiation Physics and Chemistry (2019), doi:
https://doi.org/10.1016/j.radphyschem.2019.108537.

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 Investigation of gamma ray attenuation features of bismuth

oxide Nano powder reinforced high-density polyethylene Matrix

Composites

Alyaa H. Abdalsalama, Erdem ŞAKARb, Kawa M. Kakya, c, M. H. A. Mharebd,e, Betul

CEVĐZ ŞAKARf. M. I. Sayyedg,*, Ali GÜROLb

a
Nanotechnology and Advanced Materials Research Center, University of Technology,
35010, Baghdad, Iraq
b
Ataturk University, Faculty of Science, Department of Physics, Erzurum, 25240, Turkey
c
Directorate of Communication and Information Technology, Council of Representatives
of Iraq, Conferences Palace, Baghdad, Iraq
d
Department of Physics, College of Science, Imam Abdulrahman Bin Faisal University,
P.O. Box 1982, 31441, Dammam, Saudi Arabia
e
Basic and Applied Scientific Research Center, Imam Abdulrahman Bin Faisal University,
P.O. Box 1982, 31441, Dammam, Saudi Arabia
f
East Anatolia High Technology Application and Research Center, Atatürk University,
Erzurum 25240, Turkey
g
Department of Physics, Faculty of Science, University of Tabuk, Tabuk, Saudia Arabia

Abstract:

In this work, five samples of high-density polyethylene have been made by varying

bismuth oxide (Bi2O3) concentration 0.5, 1.0, 1.5 and 2.0 wt%. Scanning electron

microscopic (SEM) has been used to analysis of the samples to point out the changes in the

surface morphology. Energy Dispersive X-ray (EDX) has been performed for evaluating

chemical composition of the prepared samples. X-ray diffraction (XRD) spectra of the pure

Bi2O3, pure high-density polyethylene (HDPE) and HDPE with different amount of Bi2O3

have been investigated. Additionally, the Raman spectroscopy of all synthesized polymer

matrix were measured to explore the different molecular groups. Finally, the mass
attenuation coefficients µ/ρ for the samples have been measured using narrow beam of

gamma-ray at eight energies between from 30.8 to 383.8 keV. The effect of the photon

energy and the addition of Bi2O3 on the gamma-ray shielding ability of the prepared

sample have been discussed. In conclusion, the prepared samples showed good attenuation

properties.

Keywords: HDPE; SEM; EDX; XRD; Mass attenuation coefficients; XCOM

*Corresponding author: mabualssayed@ut.edu.sa (M. I. Sayyed)

1. Introduction

The increasing demined of nuclear application made the safety martials against nuclear

irradiation become an important area for researchers. The shielding materials are the

materials that can absorb high energy of radiation to protect workers from the ray damage

[1-4]. Several materials were used as shielding materials used in practical applications such

as lead walls or specific types of concretes that have high-density. However, some other

materials which are well known with high density materials like; bismuth, copper, steel,

some type of glass systems with heavy metal oxides etc. However, there are some demerits

in the chemical stability, heaviness, flexibility and toxicity of the common shielding

materials. To overcome these drawbacks in lead and concrete, researchers started to

develop new types of shielding materials which are free of lead, cheap, flexible and

effective in absorbing the gamma photons by incorporation of inorganic particles such as

lead or lead oxide in polymers [5-9]. In fact, polymer composite started to be utilized in

various fields such as; automobile, aerospace, biomedical, construction and electrical

applications. Moreover, polymer composites have two phases, it can be as matrix

composite polymer, or reinforcement their properties depend on the filler type, filler

content, bonding between the reinforcement and the matrix and the preparation methods of

the composite. Different of types of polymers may be used as a matrix such as

thermoplastic, thermosets and elastomers [12-15 14]. Among shielding composite material,

the one made of epoxy resin considered the more common due to its excellent properties

such as, low shrinkage, adhesion to various reinforcements, high chemical and heat

resistance, high tensile strength and excellent absorption against gamma ray and neutron

irradiation [16, 17]. HDPE / lead oxide composite have been investigated for shielding of

gamma-rays and the results displayed good percentage of heaviness in comparison with

some conventional materials [18]. Also, hexagonal boron nitride (h-BN) and Gd2O3

nanoparticles to reinforce high density polyethylene using melt-compounding technique

were examined. Results of shielding radiations showed improvement of 14–52%, 200–

280% for gamma ray and neutron, respectively [19]. On the other hand, the same technique

to reinforce HDPE with silane-modified boron nitride and made comparison with other

composites reinforced with pristine BN and boron carbide (B4C) fillers showed the

importance of interfacial adhesion property between polymer and fillers [20]. Tayfun Bel

et.al prepared composite with improved shielding against thermal neutrons by using poly

(methyl methacrylate) (PMMA) reinforced with different concentration of composite

synthesized by in-situ polymerization [21].

In this work, by hot pressing technique we synthesized five different high-density

polyethylene (HDPE) reinforced by bismuth oxide (Bi2O3). The bismuth concentration was

0.5, 1.0, 1.5, 2.0 wt%. X-ray diffraction (XRD) spectra of the pure Bi2O3, pure HDPE and

HDPE with different amount of Bi2O3 have been investigated in this work. Also, EDX
performed in this work for investigating the semi-quantitative for all elements evolved in

the prepared composite. Further, the mass attenuation coefficients µ/ρ for the present

polymers have been measured using transmission geometry at 30.8, 35.0, 53.16, 80.8,

276.4, 302.8, 356 and 383.8 keV.

2. Experimental

2.1 Material preparation

High-density polyethylene (HDPE) polymer provided from China, with tensile strength at

break (26 MPa), with density of 0.953 g/cm3 and melt flow indexes (MFI) around 0.05

g/10 min. Bi2O3 Nano particles with average size 25 nano was used as a filler. Composites

with 0.5, 1, 1.5, and 2% weight have been prepared by using hot compression method

using specific mold. Moreover, Nano bismuth oxide and pellets of polyethylene were

carefully weighted and mixed in order to get homogenous matrix. Once we got the final

mixer we poured it in a stainless-steel with 15 cm length, 10 cm wide, and 4 mm thick.

Before pressing the composite, inner up and down of the mold were covered with two

layers of aluminum foil to make sure of getting a smooth surface. Finally, the hot press at

(110°C) for about fifteen minutes was used while 20 Mpa of hydraulic press with the

capacity of molding tooling and heating was utilized. Fig. 1 shows the final samples after

cutting with dimensions of 20 mm length, 20 mm, width, and 2 mm thickness; it clearly

shows the increment of the yellow color with increasing the concentration of Bi2O3.

2.2 Characterizations

In order to investigate the surface morphology of the fabricated polymer compositions,

SEM ZEIS Gemini Sigma 300, has been utilized to study the microstructure and chemical
element evolved in the compositions. Samples were prepared for observation by adhering

the polymer samples on a gold tape, in such case it can be measured directly without any

coating which is normally used in such conditions for running the EDX measurements.

Moreover, we measured the structural features of the Nano bismuth introduced to High

density polyethylene by using X-ray diffraction technique utilizing PANalytical/Empryean

equipment, the measuring process used in this characterization was by performing Ni-

filtered, were the Cu-Kα radiation wavelength was 1.54 nm, angle scan used was 10° per

minute, while the total profile scanned was in the region of 10°-90° with step size of 0.01.

Raman spectroscopy was utilized to study the different molecular groups, WITec alpha

300 R Micro-Raman spectrometer have been used to recorded the Raman spectra with

additional Nd:YAG laser source of 532 nm as an exciting source. Moreover, 0.3 mW laser

power was used with recording range 0-3800 cm-1, the integration time was 5 second for

every single Raman step. On the other hand and to study the photon attenuation proeprties

for the present samples, the mass attenuation coefficients (µ/ρ) have been measured using

transmission geometry. A 10 mCi 133Ba radioactive point source was utilized to get gamma

photons of 30.8, 35.0, 53.16, 80.8, 276.4, 302.8, 356 and 383.8 keV. A Canberra ultra-

LEGe detector with active diameter and area of 8 mm and 50 mm2 respectively, and Ge

crystal which has a 5mm thickness was utilized to detect the photons reaching out detector

after (I) and before (I0) attenuating in the polymer sample. Detector has resolutions of 150

eV at 5.9 keV and 550 eV at 122 keV. Additionally, a Tennelec 244 model amplifier was

utilized to amplify the pulses coming from the preamplifier of the detector. To record the

data, A Multi-Channels Analyzer (MCA) of 2048 channels has been utilized. The live time

was set to an optimum value to get suitable counting statistics (Area under peak>10000).
3. Results and discussion

3.1 SEM

In order to estimate the variations in surface morphology of the prepared samples and the

dispersion of bismuth oxide nanoparticles in HDPE matrix, the prepared samples were

subjected to scanning electron microscopic analysis. The morphology of polymer

composite depends upon different factors such as component melt viscosities, constituent’s

weight percentage, compatibility between composite constituents and processing

conditions. In a most heterogeneous system, morphology, whereby one phase is distributed

in another phase, is observed [22]. Fig. 2 shows SEM images of HDPE/Bi2O3 composite

samples at range (0 - 2) wt. %. The SEM photographs of the pristine sample shown in Fig.

2(a) clearly revealed a continuous phase of HDPE matrix with the presence of lines which

may belong to the machining process. In addition, Fig. 2 (b-c) shows SEM photographs of

the prepared composites, it clear seen from the figure that Nano filler is well embedded in

the matrix of HDPE and the matrix coverage around the filler, and this assigned to good

interfacial adhesion and compatibility between the matrix and Bi2O3NPs. This result is

well machining with Mohamed et.al [23] that used PbO NPs in recycled HDPE, at which

the good dispersity of nanoparticles in the r-HDPE matrix may belong to the increment in

the interfacial area and link to more HDPE backbone during the both processes namely the

melting and the mixing, while the opposite occurs for r-HDPE/bulk PbO composites.

Moreover, SEM photographs indicted to the uniform and homogenous distribution of

nanoparticles with no agglomeration within the polymer matrix indicating to the

successfully prepared. This homogeneity may affect the shielding properties of the samples
since the added Nano bismuth oxide has a high surface area and does not undergo any

chemical reaction instead occupies the interstitial spaces within the matrix network and

might have enhanced the attenuation ability of the composites [24].

3.2 EDX

Energy-dispersive X-ray spectroscopy (EDX) used in this work to study the semi-

quantitative for all elements evolved in the prepared composite. Fig. 3 (a-e) presents the

EDX profiles for all fabricated samples. In all samples, we can see a clear peak confirming

the availability if C (carbon) as it is the main structure of HDPE which is based on C2H4

formula. It is difficult to detect H (hydrogen) in this composite, due to the low energy peak

of Kα for hydrogen which made the recognization of this element difficult to quantify.

However, the Fig. 3 (b-e) presents the availability of bismuth in all samples 0.5%Bi2O3,

1.0%Bi2O3, 1.5%Bi2O3, and 2.0%Bi2O3. The peak obtained from bismuth found to be

increased with increasing the concentration of bismuth which is a good indication that the

composite is homogenous and the bismuth is available.

3.3 XRD

The XRD patterns of the pure Bi2O3, pure HDPE and HDPE with different amount of

Bi2O3 contents are illustrated in Fig. 4 (a and b). Apparently, the HDPE shows two peaks a

strong at 21.6° and a less intensive at 24.0°. These peaks can be attributed to the typical

orthorhombic unit cell structure of (110) and (200) reflection planes, respectively. The

obtained results confirm the previous publications [25-28]. The other weak intense peaks

appear at 30° and 36° which correspond to reflection planes (210) and (020), respectively

[27, 28]. Moreover, several weak peaks appear within range from 40°-60° [28]. The
addition of bismuth to HDPE has a slightly effect on the main peaks (110) and (200) as

shown in Fig. 4 (b), but there is no effect of bismuth on original structure of the HDPE

which can be ascribed to a little amount of bismuth contents. As it can be seen from Fig. 4

(b), the position of the main peaks (110) and (200) have slightly changed with the addition

of Bi contents which indicates that the original structure of the HDPE remains stable [29].

3.4 Raman

The Raman spectrum is an important tool for detecting the vibrational characteristics for

the bonding in metal-oxide as well as their structure. The Raman results show several

bands as illustrated in Fig. 5. and their assignments are summarized in Table 1. The bands

at (1058 cm-1) and (1125 cm-1) are referred to C-C stretching modes that vibrate the

skeletal chains as perpendicular and parallel to the chain axis, respectively. These peaks

can be utilized to reveal the load sharing on the polymer chains [30, 31]. The small and

weak band at 1080 cm-1 is attributed to the C-C stretching mode of the amorphous chains.

The large peak at 1400 cm-1 consists of three distinctive peaks centered around 1412 cm-1,

1436 cm-1 and 1457 cm-1 which ascribed to the CH2 bending modes. The band at 1412 cm-1

can be utilized to assess the direction of the crystallinity of polyethylene and crystalline

chains, this band is ascribed to the CH2 bending in the orthorhombic crystal [32-36]. The

band around 1436 cm-1 may be ascribed to the bending modes for CH2 in the amorphous

trans chains as well as the band around 1457 cm-1 is attributed to the melt-like amorphous

chains [31, 37]. It can be noted, the former peaks are located between the amorphous and

crystalline regions within the three-phase model [38, 39]. In addition, the CH2 twisting

modes of the crystalline and amorphous chains display two peaks at 1286 cm-1 and 1363

cm-1, respectively. The previous peaks can be utilized as the internal standards to assess the
molecular orientation [32, 40] and the crystallinity [34, 41]. According to previous

analyses, we can classify the Raman bands to amorphous and crystalline chain as listed in

Table 1. The bands at (1080, 1436 and 1457 cm-1) and (1058, 1125 and 1286 and 1412 cm-
1
) are assigned to amorphous chain and the crystalline chain, respectively. Fig. 6 shows the

de-convolution with Voigt functions using a nonlinear Levenberg-Marquardt method. The

de-convolution of one sample was performed within the range of 1000-1600 cm-1. The de-

convoluted spectrum shows seven bands centered at 1058, 1103, 1125, 1287, 1416, 1436

and 1458 cm-1. In addition, it can be seen the effect of metal oxide, i.e. Bi2O3 on the

polymer chain. There is no any new band appear because of Bi2O3 concentration was very

low, but all bands show enhanced in FWHM with increase in Bi2O3 concentrations. This

enhancement in FWHM for all bands may be attributed to the degree of crystallinity or

defects including oxygen vacancies [42, 43].

3.5 Gamma radiation attenuation features

The experimental transmission geometry used in this work to study the attenuation features

for the prepared samples is schematically exhibited in Fig. 7. The full details for the

experimental determination of µ/ρ is given in our recent paper [44].

The experimental values of µ/ρ measured using the transmission geometry are summarized

in Table 2. Also, we enlisted in this table the theoretical values calculated using WinXcom

program. As we can see in Table 2 the agreement is excellent at all energies and for all

samples. Also, we calculated the uncertainty in the measured µ/ρ according to the next

equation:

1 ∆  ∆   ∆  ∆ 

μ/ρ =
  +   + ln     (1)
  
where ∆I and ∆I0 are respectively the uncertainties of I and I0 intensities.

The calculated ∆µ/ρ values are given in Table 2 and it is obvious that the uncertainty in the

measurements is small, implying the precision in the experimental µ/ρ values.

Fig. 8 provided the µ/ρ of the HDPE polymer doped by 0, 0.5, 1, 1.5 and 2 Bi2O3% as a

function of photon energy (30.8–383.9 keV). In general, the µ/ρ curve shows that the

attenuation coefficients for samples were reducing as the photon was increased from

30.8keV up to 383.9 keV. However, the reduction in the µ/ρ can be divided in two regions

according to the photon energy. The first one is from 30.8 keV to 223.4 keV and the

second region from 276.4 keV to 383.9 keV. As suggested by radiation physics laws, there

are 3 processes happen when gamma photons interact with a medium (say polymer

sample). These processes are photoelectric effect (dominates in the first region in Fig. 8),

Compton scattering (dominates in the second region in Fig. 8) and pair production (this

occurs only for the energy larger than 1.022 MeV so it is excluded in this work [45]. In the

first region in the curve, the values of µ/ρ for the polymers decrease rapidly with the rise of

the energy from 30.8 keV to 223.4 keV. For example, the µ/ρ for the sample contains 2

mol% Bi2O3 decreases from 0.788 cm2/g to 0.147 cm2/g as the energy changes from 30.8

keV to 223.4 keV. This is because the cross section (which represents the probability of

interaction) of photoelectric effect is dependent on Z4-5 and E-3.5. For this reason, we can

notice the rapid decreasing in the µ/ρ values at the first energy zone. Additionally, this

explains the high µ/ρ values at this region especially at 30.8 keV where the µ/ρ attains the

maximum value at this energy. In the second energy in Fig. 8, the probability of

photoelectric is low and another process becomes the most important namely the Compton

scattering. It can be seen at this region that there is no remarkable difference in the µ/ρ
values for all polymers. The data presented in Table 2 and Fig. 8 also shows that the µ/ρ

value was increased with the addition of Bi2O3 for the prepared polymers at the nine

photon energies used in the attenuation measurements. This trend in the µ/ρ is owing to the

amplification of elemental composition of Bi2O3 within the polymer which raises the

density of the prepared polymer samples, and the density plays an obvious role in

estimating the number of attenuated photons when moving via the polymer specimen.

Moreover, since the present polymer samples are composed of three elements (H, C and

Bi), then we can study the characteristic of the polymers in terms of equivalent elements,

which is recognized as the effective atomic number (Zeff). For the prepared polymers with

different content of Bi2O3, the similar procedure used in our recent paper [46] was applied

to calculate the Zeff values between 30.82 keV-383.9 keV. The Zeff results for the HDPE

polymer doped by 0, 0.5, 1, 1.5 and 2 Bi2O3% are exhibited in Fig. 9. The Zeff curve for the

prepared polymers presented in this figure has the similar trend observed for the µ/ρ. We

can see that with the increasing of the energy from 30.8 keV to 223.4 keV, the Zeff

decreases rapidly and shows a constant trend between 276.4 keV to 383.9 keV.

Additionally, it is clear that the lowest Zeff values at all energies are observed for HDPE

without Bi2O3, while the highest Zeff are found for HDPE with 2 % Bi2O3, which suggests

that the Zeff is increasing with the addition of Bi2O3 (which is clearly seen in Fig. 9). As we

observed in the µ/ρ curve, the addition of Bi2O3 clearly affects the Zeff values at low energy

values (especially at the lowest energy 30.8 keV). For example, at 30.8 keV the Zeff for the

free Bi2O3 and 2 mol % are 3.05 and 8.60. This is because the probability of the

photoelectric interaction is dependent on Z4-5, therefore the addition of Bi2O3 (Bi has high

ztomic number) leads to increase the Zeff.

Furthermore, the half value layer (HVL) is essential shielding quantity from a practical

point of view to assess the thickness of the polymer sample needs to attenuate half of

photon intensity. Lower HVL points out thinner polymer required to attenuate 50% of

photon intensity [47]. The next equation was used to calculate the HVL for the prepared

polymers with different content of Bi2O3:

0.693
 = (2)


Fig. 10 shows the variation of HVL for the polymers with 0, 0.5, 1, 1.5 and 2 Bi2O3% as a

function of energy.

Because of the highest content of Bi in the 2.0% Bi2O3 polymer, it has lower HVL than

the rest of polymers at all energies. Additionally, the HDPE without Bi2O3 contains only H

and C and this leads to high HVL of this sample. It is evident from this figure that the HVL

depends mainly upon the density of the polymer. The higher density value, the lower HVL

is and thus the lees energy passes via the polymer sample. The HDPE with 2.0% Bi2O3 is

denser than the HDPE with 0, 0.5, 1.0 and 1.5% Bi2O3, therefore we expected that more

photons being attenuated by the HDPE with 2.0% Bi2O3, since the chances of the

interaction between the photons with the atoms of HDPE with 2.0% Bi2O3 is relatively

high in comparison with the rest of investigated polymers. Therefore, we can reach to a

conclusion that a high density polymer sample is more suitable for radiation shielding

applications. A similar finding on this density effect in gamma photons was reported by Li

et al. [48] for basalt fiber reinforced epoxy matrix composite. Besides, the HVL values of

the HDPE with different content of Bi2O3 are found to rise gradually with increase the
energy, which implies that the rise in the photon energy makes it being able of deeply

penetrating in the polymer.

4. Conclusion

In summary, the current work investigates the gamma shielding characteristics of

nanocomposite materials based on high-density polyethylene (HDPE). High density

Polyethylene/ bismuth oxide nanocomposites were fabricated using conventional Hot-

pressing technique. SEM photographs revealed better dispersion of the Nano fillers and

good compatibility with polymer matrix confirming no need for coupling agents to be

used. EDX presents the availability of bismuth in all samples 0.5%Bi2O3, 1.0%Bi2O3,

1.5%Bi2O3, and 2.0%Bi2O3. The peak obtained from bismuth found to be increased with

increasing the concentration of bismuth which is a good indication that the composite is

homogenous and the bismuth is available. The XRD analysis confirmed the presence of

both bismuth oxide nanoparticles and high-density polyethylene peaks. However, the

position of the main peaks (110) and (200) have slightly changed with the addition of Bi

contents that indicates the original structure of the HDPE remains stable. Raman

spectroscopy presents the related bands of HDPE, while there is no any new band appear

because of Bi2O3 concentration was very low, but all bands show enhanced in FWHM with

increase in Bi2O3 concentrations. This enhancement in FWHM for all bands may be

attributed to the degree of crystallinity or defects including oxygen vacancies. Radiation

shielding measurements of 2 wt % bismuth oxide nanocomposite recorded improved over

those of the neat high-density polyethylene and the other low percentage. The gamma

radiation shield of the prepared Nano composites suggests that the composite with
composition 98% HDPE / 2.0% Bi2O3 is a suitable candidate to be used in radiation

shielding applications between 30.82 keV-383.9 keV.

Acknowledgements

Authors would like to gratefully acknowledge use of the services and facilities of

Nanotechnology and Advanced Materials Research Center, University of Technology

(UOT), Baghdad, Iraq.

References

[1]. Junior, T.A.A., Nogueira, M.S., Vivolo, V., Potiens, M.P.A., Campos, L.L., 2017.
Mass attenuation coefficients of X-rays in different barite concrete used in radiation
protection as shielding against ionizing radiation, Rad. Phys. Chem. 140,pp.349-354.
[2]. Yingwei Hou , Min Li, Yizhuo Gu, Zhongjia Yang,Ran Li, Zuoguang Zhang,”Gamma
Ray Shielding Property of Tungsten Powder Modified Continuous Basalt Fiber
Reinforced Epoxy Matrix Composites”, POLYMER COMPOSITES—2017,pp.1-10.
[3]. V. Harish, N. Nagaiah, T. Niranjana Prabhu, K. T. Varughese,”Preparation and
Characterization of Lead Monoxide Filled Unsaturated Polyester Based Polymer
Composites for Gamma Radiation Shielding Applications”, Journal of Applied
Polymer Science, Vol. 112, 2009, pp.1503–1508.
[4]. M.R. Ambika, N. Nagaiah, S.K. Suman,”Evaluation of gamma shielding parameters of
bismuth oxide filled polymer composite”, Indian journal of pure and applied
physics,Vol.56,2018,pp.604-608.
[5]. Vaz, P.,”Radiological protection, safety and security issues in the industrial and
medical applications of radiation sources, Rad. Phys. Chem. 2015,116, 48–55.
[6]. Erdem, M., Baykara, O., Dogru, M., Kuluozturk, F., 2010. A novel shielding material
prepared from solid waste containing lead for gamma ray, Rad. Phys. Chem. 79, 917–
922.
[7]. Nambiar, S.; John, T. W. Y.,” Polymer-Composite Materials for Radiation Protection
“, ACS Appl. Mater. Interfaces 2012, 4, pp.5717−5726.
[8]. McCaffrey, J. P.; Shen, H.; Downton, B.; Mainegra-Hing, E.,” Radiation attenuation by
lead and nonlead materials used in radiation shielding garments”, Med. Phys. 2007, 34,
pp.530-537.
[9]. Abdel-Aziz, M. M.; Badran, A. S.; Abdel Hakem, A. A.; Helaly, F. M.; Moustafa, A.
B. “Styrene-Butadiene Rubber/ Lead Oxide Composites as Gamma Radiation
Shields”,J. Appl. Polym. Sci. 1991, 42, pp.1073-1880.
[10]. M. R. Ambika, N. Nagaiah, S. K. Suman,”Role of bismuth oxide as a reinforcer on
gamma shielding ability of unsaturated polyester based polymer composites”, J. APPL.
POLYM. SCI. 2016.
[11]. Singh, V. P.; Shirmadi, S. P.; Medhat, M. E.; Badiger, N. M.” Determination of mass
attenuation coefficient for some polymers using Monte Carlo simulation”, Vacuum
2015, 119, pp.284-289.
[12]. Gupta, M. C.; Gupta, A. P. Polymer composites; New Age International: New Delhi,
2015; Chapter 1, p 1.
[13]. Liu, T.; Lv, D.; Cao, B.; Wang, H.,” Preparation of Novel Nano/Submicrofiber
Catalyst Containing Nano-TiO2 Particles”, J. Appl. Polym. Sci. 2012, 126,pp. 1977-
1982.
[14]. Eva, H.; Andrew, A.; Akif, K. ,” Electromagnetic shielding properties of
polypyrrole/polyester composites in the 1- 18 GHz frequency range “,Synth. Met.
2006, 156, 917.
[15]. Devikala, S.; Kamaraj, P. Arthanareeshwari,” Electrical Conductivity Studies of
PVA/TiO2 Composites”,Int. Res. J. Pure Appl. Chem. 2013, 3,pp. 257-263.
[16]. Nagarjuna Reddy Paluvai, Smita Mohanty, S. K. Nayak,”Synthesis and
Modifications of Epoxy Resins and Their Composites: A Review”, Polymer-Plastics
Technology and Engineering 53(16):1723-1758.
[17]. N.Z. Noor Azman a,b , S.A. Siddiqui a , R. Hart c , I.M. Low a,n ,”Effect of particle
size, filler loadings and x-ray tube voltage on the transmitted x-ray transmission in
tungsten oxide-epoxy composites” Applied Radiation and Isotopes, 71 (2013),pp. 62–
67.
[18]. Mohamed E. Mahmoud, Ahmed M. El-Khatib,Mohamed S. Badawi, Amal R.
Rashed, Rehab M.El-Sharkawy, Abouzeid A. Thabet,” Fabrication, characterization
and gamma rays shielding properties of nano and micro lead oxidedispersed-high
density polyethylene composites”, Radiation Physics and Chemistry Vol. 145,
2018,pp. 160-173.
[19]. Ş. Gözde Đrim, A. Alchekhw Wis, M. Aker Keskin, Oktay Baykara, Guralp Ozkoc,
Ahmet Avcı, Mahmut Doğru, Mesut Karakoc,” Physical, mechanical and neutron
shielding properties of h-BN/Gd2O3/HDPE ternary Nanocomposites”, Radiation
Physics and Chemistry,Vol. 144, 2018, pp.434-443.
[20]. Ji Wook Shin, Jang-Woo Lee, Seunggun Yu, Bum Ki Baek, Jun Pyo Hong,Yongsok
Seo, Woo Nyon Kim, Soon Man Hong, Chong Min Koo,” Polyethylene/boron-
containing composites for radiation shielding”, Thermochimica Acta 585 (2014) pp.5–
9.
[21]. Tayfun Bela, Cuneyt Arslana, Nilgun Baydoganb ,”Radiation shielding properties of
poly (methyl methacrylate) / colemanite composite for the use in mixed irradiation
fields of neutrons and gamma rays”, Materials Chemistry and Physics 221 (2019)
pp.58–67.
[22]. William D. Callister Jr.,” Materials Science and Engineering: An Introduction”,
book, John Wiley & Sons, Inc, 2007, chapter 16, pp.578.
[23]. Mohamed E.Mahmoud, Ahmed M.El-Khatib, Amal R.Rashad, Rehab M.El-
Sharkawy, Abouzeid A.Thabet,” Recycled high-density polyethylene plastics added
with lead oxide nanoparticles as sustainable radiation shielding materials”, Journal of
Cleaner Production Volume 176, 2018, pp. 276-287.
[24]. M. R. Ambika,N. Nagaiah, S. K. Suman, “Role of bismuth oxide as a reinforcer on
gamma shielding ability of unsaturated polyester based polymer composites” J. APPL.
POLYM. SCI. 2016, 44657, pp. 2-7.
[25]. Chouit, Fairouz, Ounassa Guellati, Skander Boukhezar, Aicha Harat, Mohamed
Guerioune, and Nacer Badi. "Synthesis and characterization of HDPE/N-MWNT
nanocomposite films." Nanoscale research letters 9, no. 1 (2014): 288.
[26]. Grigoriadou I, Paraskevopoulos K, Chrissafis K, Pavlidou E, Stamkopoulos TG,
Bikiaris D: Effect of different nanoparticles on HDPE UV stability. Polym Degrad Stab
2011, 96:151–163.
[27]. Inci B, Wagener KB: Decreasing the alkyl branch frequency in precision
polyethylene: pushing the limits toward longer run lengths. J Am Chem Soc 2011,
133(31):11872–11875.
[28]. Trujillo M, Arnal M, Müller A, Laredo E, Bredeau S, Bonduel D, Dubois P: Thermal
and morphological characterization of nanocomposites prepared by in situ
polymerisation of high-density polyethylene on carbon nanotubes. Macromolecules
2007, 40(17):6268–6276.
[29]. Filippi S, Marazzato C, Magagnini P, Famulari A, Arosio P, Meille SV. Structure
and morphology of HDPE-g-MA/organoclay nanocomposites: effects of the
preparation procedures. Eur Polym J 2008;44(4):987e1002.
[30]. Tashiro K, Wu G, Kobayashi M (1988) Morphological effect on the Raman
frequency shift induced by tensile stress applied to crystalline polyoxymethylene and
polyethylene: spectroscopic support for the idea of an inhomogeneous stress
distribution in polymer material. Polymer 29: 1768-1778.
[31]. Kida T, Oku T, Hiejima Y, Nitta K-H (2015) Deformation mechanism of highdensity
polyethylene probed by in situ Raman spectroscopy. Polymer 58: 88-95.
[32]. Gall M, Hendra P, Peacock O, Cudby MEA, Willis HA (1972) The laser-Raman
spectrum of polyethylene: The assignment of the spectrum to fundamental modes of
vibration. Spectrochim Acta Part A Mol Spectrosc 28A: 1485-1496.
[33]. Gall M, Hendra P, Peacock C, Cudby M, Willis H (1972) Laser-Raman spectrum of
polyethylene: Part 1. Structure and analysis of the polymer. Polymer 13: 104-108.
[34]. Rull F, Prieto AC, Casado JM, Sobron F, Edwards HGM (1993) Estimation of
Crystallinity in Polyethylene by Raman Spectroscopy. J Raman Spectrosc 24: 545-550.
[35]. Strobl G, Hagedorn W (1978) Raman spectroscopic method for determining the
crystallinity of polyethylene. J Polym Sci Polym Phys 16: 1181-1193.
[36]. Migler KB, Kotula AP, Hight Walker AR (2015) Trans -Rich Structures in Early
Stage Crystallization of Polyethylene. Macromolecules 48: 4555-4561.
[37]. Luu DV, Cambon L, Lapeyre C (1980) Caracterisation des Phases dans
lePolyethylene par Effet Raman. J Raman Spectrosc 9: 172-175.
[38]. Mutter R, Stille W, Strobl G (1993) Transition regions and surface melting in
partially crystalline polyethylene: A raman spectroscopic study. J Polym Sci Part B
Polym Phys 31: 99-105.
[39]. Martin B, Jawhari T, Pastor JM, Merino JC (1996) Micro-Raman study of the
longitudinal acoustic modes (LAM) evolution along the transition front in uniaxially
stretched HDPE. Colloid Polym Sci 274: 285-289.
[40]. Bower DI (1972) Investigation of molecular orientation distributions by polarized
raman scattering and polarized fluorescence. J Polym Sci Polym Phys Ed 10: 2135-
2153.
[41]. Lin W, Cossar M, Dang V, Teh J (2007) The application of Raman spectroscopy to
three-phase characterization of polyethylene crystallinity. Polym Test 26: 814-821.
[42]. Merupo, Victor-Ishrayelu, Subramaniam Velumani, Karolina Ordon, Nicolas Errien,
Jacek Szade, and Abdel-Hadi Kassiba. "Structural and optical characterization of ball-
milled copper-doped bismuth vanadium oxide (BiVO 4)." CrystEngComm 17, no. 17
(2015): 3366-3375.
[43]. Zhou, Bin, Xu Zhao, Huijuan Liu, Jiuhui Qu, and C. P. Huang. "Visible-light
sensitive cobalt-doped BiVO4 (Co-BiVO4) photocatalytic composites for the
degradation of methylene blue dye in dilute aqueous solutions." Applied Catalysis B:
Environmental 99, no. 1-2 (2010): 214-221.
[44]. A.E. Ersundu, M. Büyükyıldız, M. Çelikbilek Ersundu, E. Şakar, M. Kurudirek, The
heavy metal oxide glasses within the WO3-MoO3-TeO2 system to investigate the
shielding properties of radiation applications, Progress in Nuclear Energy 104 (2018)
280–287.
[45]. Osman Agar, Hüseyin O. Tekin, M.I. Sayyed, Mehmet E. Korkmaz, Ozgur Culfa,
Can Ertugay, 2019. Experimental investigation of photon attenuation behaviors for
concretes including natural perlite, Results in Physics 12, 237–243.
[46]. Y. S. Rammah, M. I. Sayyed, A. S. Abohaswa, H. O. Tekin, 2018. FTIR, electronic
polarizability and shielding parameters of B2O3 glasses doped with SnO2. , Applied
Physics A, 124:650.
[47]. M.I. Sayyed, R. El-Mallawany, 2017. Shielding properties of (100-x) TeO2-(x)MoO3
glasses, Materials Chemistry and Physics 201, 50-56.
[48]. Ran Li, Yizhuo Gu, Gaolong Zhang, Zhongjia Yang, Min Li, Zuoguang Zhang,
Radiation shielding property of structural polymer composite: Continuous basalt fiber
reinforced epoxy matrix composite containing erbium oxide, Composites Science and
Technology 143 (2017) 67-74.
Table 1: Raman band assignments of the polyethylene with Bi2O3 contents.
Wavenumber (cm-1) Assignments Raman tensor
1058 Trans chain B2g + B3g
1080 Amorphous ------
1125 Trans chain Ag + B1g
1286 Crystalline B2g + B3g
1363 Amorphous ------
1412 Crystalline (orthorhombic) Ag
1436 Amorphous trans (intermediate) Ag + A1g
1457 Amorphous Ag + B1g
Table 2. The experimental values of µ/ρ measured using the transmission geometry

0.0%Bi 0.5%Bi 1.0%Bi 1.5%Bi 2.0%Bi

Energy
Exp. Std. Theo. Exp. Std. Theo. Exp. Std. Theo. Exp. Std. Theo. Exp. Std. Theo.
(keV) RD RD RD RD RD
2
(cm /g) Dev. ± (cm2/g) 2
(cm /g) Dev. ± (cm2/g) 2
(cm /g) Dev. ± (cm2/g) 2
(cm /g) Dev. ± (cm2/g) 2
(cm /g) Dev. ± (cm2/g)
30.8 0.272 0.0012 0.265 2.642 0.387 0.0034 0.396 2.273 0.501 0.0050 0.526 4.753 0.696 0.0092 0.657 5.936 0.759 0.0171 0.788 3.680
35.0 0.261 0.0067 0.244 6.967 0.318 0.0131 0.337 5.638 0.452 0.0111 0.431 4.872 0.526 0.0022 0.525 0.190 0.631 0.0019 0.618 2.104
53.2 0.219 0.0057 0.204 7.353 0.227 0.0065 0.235 3.404 0.252 0.0225 0.267 5.618 0.323 0.0344 0.298 8.389 0.311 0.0043 0.329 5.471
81.0 0.173 0.0030 0.182 4.945 0.190 0.0018 0.192 1.042 0.217 0.0023 0.202 7.426 0.217 0.0163 0.212 2.358 0.212 0.0087 0.222 4.505
223.4 0.139 0.0027 0.135 2.963 0.142 0.0008 0.138 2.899 0.148 0.0015 0.141 4.965 0.148 0.0013 0.144 2.778 0.139 0.0009 0.147 5.442
276.4 0.130 0.0011 0.125 4.000 0.123 0.0008 0.127 3.150 0.138 0.0014 0.129 6.977 0.138 0.0021 0.130 6.154 0.128 0.0006 0.132 3.030
302.9 0.123 0.0019 0.121 1.653 0.127 0.0063 0.123 3.252 0.126 0.0019 0.124 1.613 0.126 0.0014 0.125 0.800 0.122 0.0005 0.126 3.175
356.0 0.115 0.0034 0.114 0.877 0.110 0.0224 0.115 4.348 0.120 0.0225 0.116 3.448 0.120 0.0069 0.116 3.448 0.117 0.0007 0.117 0.000
383.9 0.113 0.0042 0.111 1.802 0.106 0.0205 0.111 4.505 0.117 0.0205 0.112 4.464 0.117 0.0006 0.113 3.540 0.118 0.0010 0.113 4.425

#$%&'( − #$%*+&,
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Fig. 1. Photograph of synthesized polymer composite with different concentration of Bi2O3

(a)

b
 (b)

(c)

(d)
 e

(e)
Fig. 2. SEM photographs for HDPE Nano composites (a) pure polymer (b) 0.5 wt.% Bi2O3

(c) 1.0 wt.% Bi2O3 (d) 1.5 wt.% Bi2O3 (e) 2.0 wt.% Bi2O3.

(a)
(b)

(c)
 (d)

(e)
Fig. 3. Energy-dispersive X-ray spectroscopy (EDX) profiles for all fabricated samples.
 (110)
Bi2O3
HDPE + Bi 0.0%
HDPE + Bi 0.5%
HDPE + Bi 1.0%
Intensity (a.u.)

HDPE + Bi 1.5%
HDPE + Bi 2.0%
(200)

(011)
(210)
(020)

10 20 30 40 50 60 70 80 90
2θ (degree)

(a)
 Bi2O3
HDPE + Bi 0.0%
HDPE + Bi 0.5%
HDPE + Bi 1.0%
Intensity (a.u.)

HDPE + Bi 1.5%
HDPE + Bi 2.0%

15.0 17.5 20.0 22.5 25.0 27.5 30.0

2θ (degree)

(b)
Fig. 4. XRD patterns of (a) the polyethylene with Bi2O3 contents and (b) the main two

peaks.
 HDPE + Bi 0.0%
HDPE + Bi 0.5%
HDPE + Bi 1.0%
HDPE + Bi 1.5%
HDPE + Bi 2.0%
Intensity (a.u.)

1000 1100 1200 1300 1400 1500 1600

-1
Wavenumber (cm )

Fig. 5 Raman spectrum of HDPE with different concentration of Bi2O3

 Intensity (a.u)

1000 1100 1200 1300 1400 1500 1600

-1
Wavenumber (cm )

Fig. 6. Deconvolution Raman spectrum

 Detector
connections

133
Ba point source Sample Ultra-LEGe
5 cm 5 cm
3 cm detector
Pb Pb
colimator colimator

Fig. 7. Narrow beam geometrical setup.

 0.9

0.8 Free Bi2O3

0.5% Bi2O3
0.7
1.0% Bi2O3
0.6 1.5% Bi2O3
µ/ρ (cm /g)

2.0% Bi2O3
2

0.5

0.4

0.3

0.2

0.1

0 100 200 300 400

Photon energy (keV)

Fig. 8. The mass attenuation coefficients (cm2/g) for the prepared polymers
 10

Free Bi2O3
0.5% Bi2O3
8
1.0% Bi2O3
1.5% Bi2O3
2.0% Bi2O3
Zeff

2
0 100 200 300 400
Photon energy (keV)

Fig. 9. The effective atomic number for the prepared polymers

 8
Free Bi2O3
0.5% Bi2O3
6 1.0% Bi2O3
1.5% Bi2O3
HVL (cm)

2.0% Bi2O3

0 100 200 300 400

Photon energy (keV)

Fig. 10. The half value layer (cm) for the prepared polymers
Highlights

• Five high-density polyethylene reinforced by bismuth oxide (Bi2O3) were

prepared.
• SEM has been used to evaluate the changes in the surface morphology.
• EDX performed for investigating the semi-quantitative for all elements
evolved.
• µ/ρ for has been measured using transmission geometry between 30.8 and
383.8 keV.