Materials and Design 124 (2017) 121130

Contents lists available at ScienceDirect

Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Gamma ray shielding property, shielding mechanism and predicting

model of continuous basalt ber reinforced polymer matrix composite
containing functional ller
Ran Li a, Yizhuo Gu a,, Zhongjia Yang b, Min Li a, Yingwei Hou a, Zuoguang Zhang a
a
Key Laboratory of Aerospace Advanced Materials and Performance (Ministry of Education), School of Materials Science and Engineering, Beihang University, Beijing 100191, China
b
School of Chemistry and Environment, Beihang University, Beijing 100191, China.

H I G H L I G H T S G R A P H I C A L A B S T R A C T

Adding W and Er2O3 can signicantly

improve ray shielding ability of basalt
ber reinforced composite.
Measured and calculated attenuation
coefcients are given, and their discrep-
ancy is claried based on photon inter-
action.
An empirical model is established to ac-
curately predict mass attenuation coef-
cient of the studied composite.
Functional llers modied basalt ber
composites are believed to be light-
weight structural/radiation shielding
materials.

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

Article history: Functional shielding ller modied ber reinforced polymer matrix composites are novel structural/radiation
Received 25 February 2017 shielding materials with great potentials in applications such as nuclear industry and radioactive therapy. In
Received in revised form 14 March 2017 this study, unidirectional basalt ber reinforced epoxy resin matrix composite laminates containing different
Accepted 15 March 2017
contents of tungsten (W) and erbium oxide (Er2O3) llers were fabricated. Experimental measurement and the-
Available online 16 March 2017
oretical calculation of mass attenuation coefcients of ray were carried out and analyzed based on photon
Keywords:
shielding mechanism. The effects of ller content and photon energy of ray on shielding property of composite
Fiber reinforced composite were studied. It is found that adding W and Er2O3 llers signicantly increases mass attenuation coefcient of ba-
Basalt ber salt ber composite, especially for low photon energy. The discrepancy between measured and calculated results
Epoxy resin is obvious at low ller content, and is believed to come from different considerations on penetrating photons,
Ray shielding which have undergone slight Compton scattering. The corresponding mechanism was discussed. An empirical
Shielding mechanism model based on photoelectric absorption effect, Compton scattering effect and effective atomic number is
established to modify calculated mass attenuation coefcient. A good accuracy was validated, so the model can
be used to design this kind of composite for better shielding ability.
2017 Elsevier Ltd. All rights reserved.

1. Introduction

Due to strong penetrability and hazardous effects on human body, -

Corresponding author. ray is a great risk for worker's security in nuclear power industry and ra-
E-mail address: benniegu@buaa.edu.cn (Y. Gu). dioactive therapy, therefore radiation protection design of radioactive

http://dx.doi.org/10.1016/j.matdes.2017.03.045
0264-1275/ 2017 Elsevier Ltd. All rights reserved.
122 R. Li et al. / Materials and Design 124 (2017) 121130
equipment becomes an essential issue. Recently, developments of mov-
able nuclear plant and nuclear waste disposal facility make require-
ments for light weight, structural and radiation shielding integrated
design. However, conventional shielding materials, such as concrete,
steel and lead, are heavy, toxic or low mechanical property, which are
hard to meet the strict demands of new radiation shielding design.
Researches on metal and polymer matrix composites used as radia-
tion protection materials are frequently reported [16]. For polymer
matrix composites, polymers, such as epoxy resin, polyimide, polyester
and ultra-high molecular weight polyethylene, blended with high
atomic number (Z) metallic llers and their compounds were fabricated
[710]. Low density, easy to process, multifunctional property and
designable shielding ability make polymeric composite materials great
potentials for future applications in radiation shielding of nuclear indus-
try and radioactive therapy. Moreover, it has been noticed that continu-
ous ber reinforced plastics (CFRP) have great advantages to serve as
radiation shielding and radiation resisting materials with excellent
combined functional/structural properties [11,12]. For example, carbon
ber reinforced Sm2O3/polyimide composite was fabricated for radia-
tion shielding in fusion reactor [13]. Glass ber reinforced plastics
have been employed within the international thermonuclear experi-
mental reactor fusion device [14,15]. Recently, our group has done
some works on preparing continuous basalt ber reinforced plastics
(CBFRP) modied with functional shielding llers for shielding
gamma ray, and good radiation shielding, radiation resisting and me-
chanical properties were demonstrated [16,17].
Compared with traditional homogeneous shielding materials, func-
tional shielding llers modied CFRP are multiphase, complicated ele-
ment composition (containing both light elements such as C, H, O, N
and heavy elements such as Ba, W or rare earth elements), heterogene-
ity and anisotropy, which make their shielding mechanism with ray
much more complex. For studying high-energy ray shielding property
of materials, attenuation coefcient is an important parameter, which
can be experimentally measured and theoretically calculated [18]. The
theoretical calculation of mass attenuation coefcient based on mix-
ture role by WinXCOM software is always conducted [19,20]. General-
ly, deviations between mass attenuation coefcients from experiment
and WinXCOM calculation for homogeneous materials are lower than
10% [18,2123], showing good agreement. However, for CFRP the devi-
ations of mass attenuation coefcient against -ray between experi-
mental and theoretical results might be large due to more complex
shielding process. For example, for CBFRP and rare earth oxide modied
CBFRP, we found that the deviation was up to 26% [17,24]. The obvious
deviations are attributed to nonhomogeneous structure and multiphase
of the composites, and make mixture role and WinXCOM method
unsuitable to predict -ray shielding performance of these kinds of
composites. This issue results in the increases of shielding property
test and difculty in reliable evaluation for shielding design with the
composites. Thus, revealing the difference of -ray shielding property
between composite and homogeneous shielding materials, understand-
ing shielding mechanism of this composite and correcting the model of
theoretical calculation are very essential.
In this study, unidirectional basalt ber reinforced epoxy resin ma-
trix composite laminates containing different contents of functional
shielding llers were fabricated by hot-press process. Considering fre-
quent employment in -ray shielding composites [7,9], heavy metallic
ller of tungsten (W) and rare earth compound of erbium oxide
(Er2O3) were selected as functional shielding llers. Mass fractions of
ber, resin matrix and functional llers in these laminates were mea-
sured. Experimental measurement and theoretical calculation of mass
attenuation coefcient against -ray with different photon energies
were carried out. -Ray shielding mechanism of W and Er2O3 modied
composites was analyzed using ray interaction theory and WinXCOM
software. Based on the effects of changing proportion of photoelectric
absorption and Compton scattering effect, and effective atomic number
on the differences between theoretical and measured mass attenuation
coefcients, an empirical equation was developed to correct theoretical
results of mass attenuation coefcients.
2. Theoretical background
2.1. Theory for calculation of mass attenuation coefcient
When a beam of monochromatic radiation having initial intensity I0
passes through a medium, the intensity of the beam will be attenuated
according to exponential attenuation law (Lambert-Beer law) which
can be expressed as [25]:
I I 0 ex
1
where I0 and I represent incident and transmitted intensity respectively,
x is sample thickness (cm), is linear attenuation coefcient (cm1),
is density (g/cm3) and / is mass attenuation coefcient (cm2/g).
The mass attenuation coefcient / indicates the probability of in-
teraction of photons with material. Classically theoretical mass attenua-
tion coefcient (/)theo for any chemical compound or mixture is given
by [18]:
   
i 2
theo i i
where i and (/)i stand for mass fraction and mass attenuation coef-
cient of constituent element or compound i, respectively. It is a style of
mixture rule.
WinXCOM software is developed by National Institute of Standard
and Technology of United States based on photon cross section database
[26]. It is a convenient approach to generate mass attenuation coef-
cients in theoretical way for compounds or mixtures in photon energies
ranging from 1 keV to 100 GeV. Based on these values and Formula (2),
total theoretical mass attenuation coefcient of materials can be calcu-
lated by this software. This method has been widely used for
charactering radiation shielding ability of materials [20,27,28].
Generally, interactions between material and -ray include photo-
electric absorption, Compton scattering and pair-production effect
[29]. For photoelectric effect, a photon is absorbed by an atom and one
of the atomic electrons, known in this case as a photoelectron, is re-
leased. Compton scattering is the process by which a photon scatters
from a nearly free atomic electron, resulting in a less energetic photon
and a scattered electron carrying the energy lost by the photon. The
third interaction is pair production, in which a photon creates an
electron-positron pair, and the photon disappears in this process.
There is an energy threshold of 1.022 MeV to generate two generated
electrons for this process, and in general pair production is important
only for photons of high energy [30].
Furthermore, total attenuation coefcient is dened by summation
of these effects, which is given as [31]:
       
3
total pe comp pair
where , and are mass attenuation coefcients of pho-
pe comp pair
toelectric absorption, Compton scattering and pair-electron effect, re-
spectively. Photon energies investigated in this study are below the
threshold of pair production, so in this study the interactions between
composite and -ray can be simplied as:
     
4
theo pe comp
In this research, WinXCOM software was employed to calculate total
theoretical mass attenuation coefcient of CBFRP. In addition, separated
 R. Li et al. / Materials and Design 124 (2017) 121130 123

Fig. 1. Manufacturing process and typical ller distributing situations of functional ller modied basalt ber composites.

mass attenuation coefcients of photoelectric absorption and Compton by School of Applied Science and Health Innovations Research Institute,
scattering were also outputted using this software. RMIT University in Australia.

2.2. Calculation of effective atomic number 3. Experimental

Effective atomic number is a parameter of photon interaction, when
photon interaction of certain compound or mixture is equivalent to cer-
tain elementary substance and atomic number of this elementary sub-
stance is dened as the effective atomic number of that compound or
mixture [32]. Being fundamentally connected with radiation interaction
process, effective atomic number has direct applications in characteriza-
tion of dosimeters, surrogate materials and biological tissues, shielding
materials for medical, nuclear engineering and radiation protection
[33]. Effective atomic number (Zeff) is generally calculated as follows:
 
f i Ai
i and Er2O3 with grain size of 57 m is provided by Beijing Founde Star
Z eff  i
Ai
fi
i Zi i
where fi is fractional abundance of element i relative to the number of
atoms providing that fi = 1, Ai is atomic weight, and Zi is atomic num-
ber. (/)i is mass attenuation coefcient of constituent element i. In this
study, a software named Auto-Zeff for computation of effective atomic
numbers was used [33,34]. Auto-Zeff is used for calculating Zeff of mate-
rial according to element compositions, and the software is developed
3.1. Laminate preparation
For resin matrix, DGEBA (Diglycidyl ether of bisphenol A) epoxy
resin produced by Nantong Xingchen Synthetic Material Co. Ltd. and
BC12 curing agent supplied by Dasen Material Technology Co. Ltd.
were selected. For ber reinforcement, due to containing high Z compo-
sition, such as FeO, Fe2O3, MnO and BaO [38], basalt ber exhibits certain
shielding capability against ray [17], so 300 g/m2 unidirectional basalt
ber fabric provided by Shanxi Basalt Fiber Co. Ltd. was used. W and
Er2O3 particles in micron size were selected as functional llers. W
with grain size of 23 m is provided by Boxin Alloy Materials Co. Ltd.
5
Science & Technology Co, Ltd. W and Er2O3 llers are both in purities
of 99.9%.
Composite laminates were prepared by hand lay-up and hot-press
process. Manufacturing process of these composite laminates is illus-
trated in Fig. 1. Unidirectional basalt fabrics were rstly impregnated
by epoxy resin mixed with W or Er2O3. Weight ratio between DGEBA
and BC12 was 100:84. Impregnated ber fabrics with ller modied
resin were laid up in unidirectional sequence. The number of fabric
layers was 7. The proportions of W particles for prepared resin were

Fig. 2. Schematic of equipment for examination of photon shielding property.

124 R. Li et al. / Materials and Design 124 (2017) 121130

Fig. 3. Metallographs of cross sections of BW and BE composites: a, BW-1, 1.7 vol%; b, BW-4, 9.3 vol%; c, BW-5, 14.4 vol%; d, BE-2, 2.1 vol%; e, BE-4, 9.7 vol%; f, BE-5, 14.0 vol%.

15, 30, 50, 150, 200 phr and those of Er2O3 were 5, 15, 25, 100, 150 phr.
Then the preforms were hot-pressed in resin bleeding process, as illus-
trated in Fig. 1. The curing procedure was 80 C for 30 min, 120 C for 3 h
and 0.6 MPa applied at 116 C. The laminates containing W particles
were noted as BW-1, BW-2, BW-3, BW-4, BW-5 with increase of ller
content, and those laminates containing Er2O3 particles were noted as
BE-1, BE-2, BE-3, BE-4, BE-5 with increase of ller content. The compos-
ite without any ller was named as BF. In addition, the prepared
laminates were cut to the dimension of 3.0 cm 3.0 cm for -ray
shielding test.
3.2. Composition measurement
In order to theoretically calculate mass attenuation coefcient of
CBFRP, mass fractions of functional llers, resin matrix and basalt ber
need to be measured. Firstly, BW and BE composites were cut into

Fig. 4. Mass fractions of composite components including basalt ber, resin and functional ller: a, BW composites, b, BE composites.
 R. Li et al. / Materials and Design 124 (2017) 121130
Fig. 5. Comparison between theoretical and experimental mass attenuation coefcients of composites: a, BW composite; b, BE composite.
dimension of 3 cm 1 cm. According to dimension and weight of sam-
ples, areal density of unidirectional BF fabric and number of layers, mass
fraction of basalt ber was calculated. Then, these samples were ablated
in mufe furnace under 500 C for 3 h to burn out resin matrix. For BE
composites, due to thermal stability of basalt ber and Er2O3 ller
under high temperature, the remnants of ablation were basalt ber
and Er2O3 particles. By weighting the remnants and subtracting weight
of basalt ber, mass fraction of Er2O3 llers was calculated. Then, mass
fraction of resin matrix was further obtained.
For BW composite, on account of oxidation effect of W ller, the
remnants of ablation were basalt ber and WO3, so on calculating
mass fraction of W ller, the weight of WO3 should be converted to W
according to its chemical formula.
3.3. Microstructure observation
To evaluate ller distribution in composites, cross-sections of BW-1,
BW-4, BW-5 and BE-2, BE-4, BE-5 composites were grinded and
polished to metallographic level [35,36]. Optical microscope was used
to characterize the distribution of W and Er2O3 llers in composites
with magnication of 100.
3.4. -Ray shielding property test
Photon shielding property of composite laminates was evaluated by
mass attenuation coefcient using a NaI(Tl) scintillation detector.
Amplied signal from the detector was recorded by a Multi-Channel
Analyzer (MCA) communicating with PC by ADMCA 2.0 software.
Schematic view of the experimental setup is shown in Fig. 2.
Radioactive sources of 133Ba and 137Cs with radioactivity of 5 Ci
were used to generate ray with energies of 356 keV and 662 keV, re-
spectively. During the test, ray generated by radioactive sources
went through 6 mm 3 cm hole of a lead collimator to form a photon
beam, and the -ray beam interacted with composite samples. A pro-
portion of -ray were scattered and absorbed by the samples, while
the rest transmitted samples and were received by NaI(Tl) detector
through 6 mm 1.5 cm hole of a lead plate. -Ray counts at region
of characteristic peak were measured by MCA software for xed time.
Fig. 6. Illustration of actual interactions between photons and materials.
125
Photon count without samples placed was noted as I0. For each sample,
three different thicknesses of around 0.5, 1 and 2 cm were tested by
changing number of composite laminates, and the transmitted counts
were noted as I1, I2 and I3, respectively. By linear tting scatter diagram
of -ln(Ii/I0) versus sample thickness t (cm), linear attenuation coefcient
(cm1) was obtained from slope of the tting line. Eventually, by mea-
suring density of samples (g/cm3) via Archimedes drainage method,
experimental mass attenuation coefcient ( ;cm2/g) was acquired.
mea
4. Results and discussion
4.1. Effect of ller content on microstructures of composites
In order to illustrate the distribution of functional llers,
metallographs of typical composites with similar ller volume fractions
are presented in Fig. 3. The golden yellow phases in Fig. 3a, b and c de-
note W llers and the phases with light color in Fig. 3d, e and f are Er2O3
llers. Based on Fig. 3, two typical ller distributing situations are illus-
trated in Fig. 1. In low ller mass fraction, due to smaller size of ller
compared with the gaps among basalt ber bundles and laments, ller
particles inltrated into ber fabric along with resin ow during hot
press process and distributed randomly among basalt bers, as shown
in Fig. 3a and b. It is similar to the ller distributing situation of Region
2 illustrated in Fig. 1. As ller content increased, large amount of ller
particles condensed between fabric layers, making them difcultly
ow into the gaps of bers and disperse among bers. Therefore, llers
aggregated between ber fabric interlayer, resulting in formation of
resin and ller rich areas as shown in Fig. 3b, c, e and f for both BW
and BE composites. This aggregation of llers is illustrated as ller dis-
tributing situation of Region 1 in Fig. 1.
4.2. Effect of ller content on mass fractions of ber and resin matrix
In order to predict radiation shielding ability using WinXCOM
software based on Formula (2), the effect of functional ller on mass
fractions of other two components, i.e. resin matrix and basalt ber,
should be known. Thus, mass fractions of these three phases are
126 R. Li et al. / Materials and Design 124 (2017) 121130

Fig. 7. Variations of theoretical mass attenuation coefcients with photon energy ranging from 0.01 MeV to 1 MeV of BW composites: a, ; b, and .
theo pe comp

shown in Fig. 4. For both composites containing W and Er2O3 llers, In addition, continuous solid curves in Fig. 5 represent and
theo
with increase of ller mass fraction, functional ller occupies the spaces they were calculated by WinXCOM software based on the mass frac-
among bers, which results in deceases of mass fractions of ber and tions of three phases in Fig. 4. The curves show similar changing
resin matrix. It also can be seen that with increase of ller content, the theo

decreasing rate of ber is larger than that of resin matrix, which is trend with the corresponding curves. However, it also can be
mea
owing to requirement of extra amount of resin to occupy the gaps seen that is larger than at same photon energy and ller
theo mea
among particles. In order to summarize the changing trend of mass frac- content, and the discrepancy between and decreases
theo mea
tions as input parameters for theoretical calculation of mass attenuation
with increase of W and Er2O3 content for both 356 and 662 keV -ray.
coefcient by means of WinXCOM, the scatter diagrams were linear
For further evaluation, this difference is dened as :
tted. The tting curves and their formulas are also illustrated in
Fig. 4. Accepted tting degree can be seen. It should be noticed that ller  
aggregation occurs in high ller content, but the linear correlations are  

not changed.  theo 6

mea

4.3. Analysis of interaction between ray and composites
Fig. 5 illustrates theoretical mass attenuation coefcients
theo
experimental results versus ller content. The scatters in Fig. 5
mea
represent of prepared laminates with different ller contents
mea
measured by testing setup as shown in Fig. 2 and standard deviations
of are also given based on statistical uctuation of photon counts.
mea
In order to show the variation of , the data were linear tted, as
mea
shown in Fig. 5. With the increase of ller content, of BW and BE
mea
composites at 356 and 662 keV both increase. By blending W and Er2O3
llers with contents up to 65.3 wt% (14.4 vol%) and 45.8 wt% (14.0 vol%)
respectively, the corresponding at 662 keV -ray reaches
mea
0.083 cm2/g and 0.073 cm2/g, while the corresponding ones at
356 keV -ray are 0.169 and 0.131 cm2/g. It indicates that adding W ll-
er has stronger effect on improving shielding ability of composite than
adding Er2O3 at similar ller volume fraction, which is attributed to ro-
bust photoelectric absorption ability of element W.
In the case of theoretical calculation, can be evaluated by
theo
adding up the effects of photoelectric absorption and Compton scatter-
and ing, as shown in Formula (4). While for actual radiation shielding, inter-
actions between materials and photons are more complicated than the
situation in the theoretical calculation. There are generally four situa-
tions when photons inject into materials during actual radiation
shielding, as shown in Fig. 6:
(1) Photon penetrates materials and no interaction takes place;
(2) Photon is absorbed directly through photoelectric effect;
(3) Photon undergoes slight Compton scattering and penetrates ma-
terials;
(4) Photon undergoes several times of Compton scattering effect and
is eventually absorbed through photoelectric effect.
In experiment, the penetrated photons of interactions 1 and 3 in
Fig. 6 are detected by NaI(Tl) detector, while during theoretical calcula-
tion, the penetrated photons from interactions 3 are regarded as
shielded ray. On account of these extra penetrated photons detected

Fig. 8. Variations of theoretical mass attenuation coefcients with photon energy ranging from 0.01 MeV to 1 MeV of BE composites: a, ; b, and .
theo pe comp
 R. Li et al. / Materials and Design 124 (2017) 121130 127

Table 1 Fig. 7a shows the variation of with photon energy ranging

Theoretical photoelectric absorption and Compton scattering mass attenuation coef- theo

cients of the studied composites and typical metal materials at photon energies of 356 from 0.01 MeV to 1 MeV of BW composites containing different con-
and 662 keV. tents of tungsten ller. Fig. 7b illustrates the variation of and
pe
Materials Compton scattering Photoelectric Percentage of of BW composites versus photon energy in the same scale.
comp
( , cm2/g) absorption photoelectric
comp
( , cm2/g) absorption From Fig. 7a, it is known that by blending W ller in resin matrix,

pe
(Wp, %) of BW composites obviously increases at photon energy ranging
theo
356 keV from 0.01 MeV to 1 MeV. In Fig. 7b, exhibits a bit of decrease
comp
Al 9.58E-02 3.47E-04 0.36
304 steel 9.21E-02 4.36E-03 4.52
with increase of ller content, so the improvement of photon attenua-
BF 1.01E-01 5.63E-04 0.55 tion ability of BW composites is attributed to signicant increase of
BW-1 9.79E-02 2.19E-02 18.24 , especially at 69.5 keV k-edge of W element, as shown in Fig. 7.
pe
BW-2 9.58E-02 3.47E-02 26.57
BW-3 9.37E-02 4.64E-02 33.13 Fig. 8a shows the curve of versus photon energy for BE com-
theo
BW-4 8.91E-02 7.57E-02 45.95 posites containing different contents of Er2O3 ller at photon energy
BW-5 8.62E-02 9.08E-02 51.32
BE-1 1.01E-01 4.95E-03 4.66
ranging from 0.01 MeV to 1 MeV. Fig. 8b illustrates the variation of
BE-2 1.01E-01 9.48E-03 8.61 and of BE composites versus photon energy in the same en-
pe comp
BE-3 9.92E-02 1.50E-02 13.15
ergy range. Adding Er2O3 has similar effect as W ller on photon atten-
BE-4 9.48E-02 3.39E-02 26.32
BE-5 9.27E-02 4.30E-02 31.68 uation ability of composites, and the maximum improvement of is
pe

662 keV at photon energy of 57.4 keV, where k is edge of Er element.

Al 7.43E-02 6.56E-05 0.09 To quantitatively characterize the contributions of photoelectric ab-
304 steel 7.16E-02 8.54E-04 1.18 sorption and Compton scattering on photon attenuation at energies of
BF 7.85E-02 1.10E-04 0.14
BW-1 7.60E-02 4.86E-03 6.01
356 and 662 keV, and were obtained by interpolation in
pe comp
BW-2 7.45E-02 7.72E-03 9.40 Figs. 7 and 8. The results are shown in Table 1, and percentage of photo-
BW-3 7.29E-02 1.03E-02 12.42 electric absorption (Wp) is also listed, which was calculated as:
BW-4 6.96E-02 1.69E-02 19.52
BW-5 6.75E-02 2.03E-02 23.08  
BE-1 7.84E-02 1.07E-03 1.35
BE-2 7.80E-02 2.07E-03 2.58 pe
Wp    100% 7
BE-3 7.69E-02 3.28E-03 4.09
BE-4 7.37E-02 7.41E-03 9.13 theo
BE-5 7.22E-02 9.42E-03 11.54

To compare with isotropic metallic materials, data of aluminum and

from interaction 3, is smaller than . Therefore, the interaction
mea theo
3 in Fig. 6, which should be strongly affected by nonhomogeneous struc-
ture and multiphase of the studied composites, is believed to be a main
reason for generating . It should be noticed that these scattered and
transmitted photons from interaction 3 are also harmful to surrounding
environment, so this proportion of photons should be counted as trans-
mitted in the view of photons radiation protection. Due to similar situ-
ation with actual application of shielding materials, the experimental
mass attenuation coefcient is more reliable and safer for characterizing
shielding property than the theoretical one.
In order to further analyze the reason for decrease of with in-
crease of ller content (see Fig. 5), total, photoelectric absorption and
Compton scattering attenuation coefcients of the studied composites
were calculated by WinXCOM, which are shown in Figs. 7 and 8.
304 steel are also listed in Table 1.
After adding W and Er2O3 llers, of composites remarkably in-
pe
creases up to one or two magnitudes. This prominent increase of photo-
electric absorption is owing to k-edge of W and Er elements at 69.5 and
57.4 keV, respectively. However, of composites slightly decreases
comp
with increase of ller content, which is resulted from low Compton scat-
tering cross section of high Z elements [37]. For BW composites against
ray of 356 keV, Wp increases from 18.24% to 51.32% as W content in-
creases from 15.30 wt% to 65.29 wt%, while Wp against 662 keV in-
creases from 6.01% to 23.08%. For BE composite against ray of
356 keV, Wp increases from 4.66% to 31.68% as Er2O3 content increases
from 4.82 wt% to 45.79 wt%, and Wp against 662 keV increases from
1.35% to 11.54%. Thus, even though Compton scattering effect weakens
for high functional ller content, remarkably increasing photoelectric
absorption leads to increase of . In addition, for aluminum and
theo

Fig. 9. Variations of effective atomic number with photon energy from 0.01 MeV to 1 MeV for different composites: a, BW composites; b, BE composites.
128 R. Li et al. / Materials and Design 124 (2017) 121130
Table 2
Zeff of BW and BE composites at 356 and 662 keV.
Composite Zeff
356 keV
BW-1 8.69
BW-2 10.51
BW-3 12.81
BW-4 18.84
BW-5 25.55
BE-1 6.23
BE-2 6.45
BE-3 7.33
BE-4 10.71
BE-5 13.00
304 steel, their Wp are no more than 5% and 2% at 356 and 662 keV,
respectively. The major compositions of 304 steel and aluminum are
elements Fe and Al respectively, which have lower photoelectric ab-
sorption abilities compared with elements Er and W. Thus, composites
blended with W and Er2O3 exhibit higher Wp than them.
Higher probability of photoelectric absorption and lower probability
of Compton scattering in case of high functional ller content result in
lower proportion of photons penetrating composite after slight Comp-
ton scattering, i.e. the interaction 3 in Fig. 6. Eventually, lower of
high ller content loaded composites is obtained, as shown in Fig. 5.
4.4. Evaluating shielding ability of composites using Zeff
Effective atomic number, Zeff, makes the interactions between ray
and shielding materials integrate to single parameter. The purpose for
calculating Zeff is to regard BW or BE composites as certain elementary
substances, which have atomic numbers of Zeff and exhibit same photon
interacting feature as the composites. Zeff of BW and BE composites
quantitatively represents photon shielding ability of composites.
Zeff of BW and BE composites was calculated by Auto-Zeff software in
this study and the results are given in Fig. 9. Unlike elementary sub-
stance, which has xed atomic number Z and does not uctuate with
change of photon energy, the composites exhibit various Zeff associated
with photon energy. As the contents of W and Er2O3 llers increase, Zeff
of BW and BE composites prominently rises in low energy region (0.05
to 0.5 MeV). The strong photoelectric absorption abilities of high Z
elements (W and Er) and the sharp enhancements of photoelectric
absorption at k-edge of W and Er make this prominent rise.
Table 2 is the Zeff of composites calculated by Auto-Zeff software at
356 and 662 keV. With increase of ller content, the Zeff at 356 and
662 keV both increase, which agree with the analysis on Fig. 9. For
BW-5 and BE-5 composites with similar ller volume fractions about
14%, Zeff of BW-5 composite is remarkably larger than that of BE-5,
Fig. 10. Correlation analysis between Wp and of composite at different photon energies: a, 356 keV; b, 662 keV.
indicating higher efciency of W ller in improving radiation shielding
ability of basalt ber reinforced composites.
662 keV
4.5. Empirical model of
7.41
8.31
To further analyze the correlation between Wp and of the stud-
9.55 ied composites, the scattered graph is illustrated in Fig. 10. Fig. 10 shows
12.59 negative correlation between Wp and , which agrees with the for-
16.89
5.97 mer analysis in Section 4.2. Reciprocal correlation is appropriate to de-
5.97 scribe the changing trend of scatters, so the reciprocal relationship
6.52 between Wp and is assumed.
8.47
9.80 To predict of composites, the correlation between Wp and Zeff
was also analyzed. On account of adding W and Er2O3 ller, dramatic in-
crease of photoelectric absorption results in better radiation shielding
performance, which also presents as higher Zeff of functional llers mod-
ied composites. In Fig. 11, the scatter diagrams of Wp versus Zeff are
shown. It is observed the scatters of BW and BE composites comply
with same law at 356 and 662 keV respectively. The scatters of BW
and BE composites can be tted quite well by logarithmic tting formu-
la, as shown in Fig. 11.
The relationship between Wp and Zeff obtained from Fig. 11 is based
on the theoretical calculation of composites. In case of experimental
measurement, shielding mechanism of composites is more complicated,
as described in Section 4.2, so it generates the difference between mea-
sured and calculated mass attenuation coefcients, i.e.. Because
strongly depends on the different percentages of photoelectric effect be-
tween experiment and theoretical calculation and the results are ob-
tained in Fig. 10, Wp is multiplied by to describe experimental
situation. The relationship between Wp  and Zeff is considered to
be a modication of theoretical one. In Fig. 12, the scatter diagrams of
Wp  versus Zeff are given, and similar proles are shown as
those in Fig. 11, which are also well tted by logarithmic tting
formulas.
Thus, according to the tted formula between Wp  and Zeff, it
comes to an empirical equation to predict as follows:
  

A  ln B  ln Z eff
8
Wp
where A and B are two empirical parameters. According to the tting
curves, A equals to 0.819 and parameter B is 0.600 at 356 keV, while A
equals to 0.500 and B is 0.581 at 662 keV.
It is known from Fig. 12 that this empirical equation is suitable to ba-
salt ber composites modied with W and Er2O3 llers. However, data
of aluminum and 304 steel are also presented in Fig. 12, which do not
fall on the curves of composites. That is resulted from different elemen-
tal compositions of aluminum and 304 steel compared with BE and BW
 R. Li et al. / Materials and Design 124 (2017) 121130 129

composites. For example, 304 steel consists of elements Cr, Ni, Fe, while
for BW composite, elements C, H, O, N, Al, Si, Fe, W exist. In addition, alu-
minum and 304 steel are homogenous materials, and the studied com-
posites have features of nonhomogeneous structure, which is believed
to be an important factor to generate the difference.
For a composite modied with certain content of llers (W or Er2O3),
by inputting the mass fractions of ber, ller and resin matrix, then
, Wp and Zeff can be calculated by WinXCOM and Auto-Zeff soft-
theo
ware. By plugging these parameters into Formula (8), modied mass at-
tenuation coefcient can be obtained.
In order to verify applicability of this empirical equation, data of BW-
3 and BE-3 composites were used, which were not involved in the for-
mer tting. From the empirical equation of the composites, of
BW-3 composite is 1.091 and 1.051 at 356 and 662 keV, respectively,
while of BE-3 composite is 1.109 and 1.049. Then, the of
theo
BW and BE composites (listed in Table 3) was corrected according to
the calculated from the empirical equation, so the corrected theo-
retical mass attenuation coefcients (named as corrected ) were Fig. 11. Proles of Wp vs. Zeff for the studied composites.
theo
obtained, as shown in Table 3. These results show that corrected
theo
is much closer to than . After correction, with respect to
mea theo
BW-3 composite, the difference between measured and calculated theoretical calculation. In addition, the discrepancy between
mass attenuation coefcients decreases from 4.4% to 0.6% at 356 keV and decreases with increase of W and Er2O3 con-
theo mea
and from 8.8% to 0.2% at 662 keV. For BE-3 composite, the difference de- tent. It is found that modication by functional llers leads to
creases from 10.8% to 0.2% at 356 keV and from 11.7% to 6.4% at 662 keV. lower proportion of photons penetrating composite after slight
These results demonstrate that the empirical equation is useful to mod- Compton scattering, which makes smaller in high ller con-
ify theoretical mass attenuation coefcient of the studied composites,
tent.
and mixture role and WinXCOM software can more accurately predict
(3) An empirical model is developed based on the relationship
radiation shielding property of composites.
among, Wp and Zeff of composite. It is used to modify theoret-
For the prepared composites in this paper, by blending high Z func-
tional llers in resin matrix, photoelectrical absorption percentage (Wp) ical mass attenuation coefcient, so mixture role and
of composites is dramatically improved and the goals of lightweight, WinXCOM software can more accurately predict radiation
shielding/structural integration can be achieved. For example, com- shielding property of the studied composite.
pared with 304 steel, BW-5 composite gives 43% weight reduction (4) Heavy metal and rare earth llers modied basalt ber rein-
with equivalent shielding ability against 356 keV -ray, and the strength forced polymer matrix composites have obviously enhanced
of BW-5 is about 644 MPa, which is larger than that of 304 steel photoelectrical absorption effect, and the advantages of light-
(620 MPa). Therefore, functional llers modied CBFRP exhibit great weight, shielding/structural integration can be achieved.
potential as future lightweight and high efcient shielding materials.
Using the proposed empirical model for Wp  vs. Zeff, ray Acknowledgement
shielding ability of this kind of composite can be theoretically evaluated,
This work was supported by the National 973 Program of China
which is meaningful for material design and optimization.
(Grant No. 2014CB931802).

5. Conclusion

In this study, unidirectional basalt ber reinforced epoxy resin ma-

trix composite laminates containing different contents of W and Er2O3
llers were fabricated by hot-press process. Mass fractions of ber,
resin matrix and functional ller of the composites and their distribu-
tions were characterized. The experimental measurement and theoret-
ical calculation of mass attenuation coefcient for ray were carried
out. The shielding mechanism of composite was discussed and an em-
pirical equation was established to modify the calculated mass attenua-
tion coefcient. The major conclusions are listed:

(1) By blending W and Er2O3 llers, the shielding performance of

composites can be prominently improved. With the increase of
ller content, of composites increases. The composites
mea
show better shielding ability at 356 keV than 662 keV. Mean-
while, W ller indicates stronger effect on improving shielding
ability of composites than Er2O3, which is attributed to robust
photoelectric absorption ability of element W.
(2) is larger than for all studied composites at same
theo mea
photon energy. It is mainly owing to the different treatments Fig. 12. Proles of the product of Wp and vs. Zeff for the studied composites and typical
on penetrated photons in experiment measurement and metal materials.
130 R. Li et al. / Materials and Design 124 (2017) 121130

Table 3 [17] R. Li, Y.Z. Gu, G.L. Zhang, Z.J. Yang, M. Li, Z.G. Zhang, Radiation shielding property of
Calculated mass attenuation coefcients with and without correction from Formula (8) for structural polymer composite: continuous basalt ber reinforced epoxy matrix
composite containing erbium oxide, Compos. Sci. Technol. 143 (3) (2017) 6774.
BW-3 and BE-3 composites.
[18] N. Singh, K.J. Singh, K. Singh, H. Singh, Comparative study of lead borate and bismuth
lead borate glass systems as gamma-radiation shielding materials, Nucl. Inst.
Photon energy/keV Composite Corrected
theo theo mea Methods Phys. Res. B 225 (3) (2004) 305309.
[19] K.J. Singh, N. Singh, R.S. Kaundal, K. Singh, Gamma-ray shielding and structural
356 BW-3 composite 0.1467 0.1396 0.1405
properties of PbO-SiO2 glasses, Nucl. Inst. Methods Phys. Res. B 266 (6) (2008)
BE-3 composite 0.1142 0.1029 0.1031 944948.
662 BW-3 composite 0.0853 0.0782 0.0784 [20] N. Singh, K.J. Singh, K. Singh, H. Singh, Gamma-ray attenuation studies of glass
BE-3 composite 0.0802 0.0764 0.0718 system, Radiat. Meas. 41 (1) (2006) 8488.
[21] B. Buyuk, A.B. Tugrul, Comparison of lead and WC-Co materials against gamma irra-
diation, Acta Phys. Pol. A 125 (2) (2014) 423425.
[22] A. Akkas, A.B. Tugrul, B. Buyuk, A.O. Addemir, M. Marsoglu, B. Agacan, Shielding
effect of boron carbide aluminium metal matrix composite against gamma and neu-
tron radiation, Acta Phys. Pol. A 128 (2B) (2015) 176180.
References [23] S. Chen, M. Bourham, A. Rabiei, Novel light-weight materials for shielding gamma
ray, Radiat. Phys. Chem. 96 (2014) 2737.
[1] S. Nambiar, J.T. Yeow, Polymer-composite materials for radiation protection, ACS [24] Y. Dong, S.Q. Chang, H.X. Zhang, C. Ren, B. Kang, M.Z. Dai, Y.D. Dai, Effects of WO3
Appl. Mater. Interfaces 4 (11) (2012) 57175726. particle size in WO3/epoxy resin radiation shielding material, Chinese Phys. Lett.
[2] S.A. Thibeault, J.H. Kang, G. Sauti, C. Park, C.C. Fay, G.C. King, Nanomaterials for 29 (10) (2012) 14.
radiation shielding, MRS Bull. 40 (10) (2015) 836841. [25] F. Akman, R. Durak, M.F. Turhan, M.R. Kacal, Studies on effective atomic numbers,
[3] S. Xu, M. Bourham, A. Rabiei, A novel ultra-light structure for radiation shielding, electron densities from mass attenuation coefcients near the K edge in some
Mater. Des. 31 (4) (2010) 21402146. samarium compounds, Appl. Radiat. Isot. 101 (2015) 107113.
[4] G.H. Fan, L. Geng, G.S. Wang, Z.Z. Zheng, A novel radiation protection material: [26] M. Berger, J. Hubbell, XCOM: Photon Cross Sections, NBSIR, 1987.
BaPbO3/Al composite, Mater. Des. 30 (3) (2009) 862866. [27] L. Gerward, N. Guilbert, K.B. Jensen, H. Levring, WinXCom-a program for calculating
[5] S. Kobayashi, N. Hosoda, R. Takashima, Tungsten alloys as radiation protection ma- X-ray attenuation coefcients, Radiat. Phys. Chem. 71 (3) (2004) 653654.
terials, Nucl. Instrum. Methods Phys. Res., Sect. A 390 (3) (1997) 426430. [28] V.P. Singh, M.E. Medhat, S.P. Shirmardi, Comparative studies on shielding properties
[6] S. Nambiar, E.K. Osei, J.T. Yeow, Polymer nanocomposite-based shielding against di- of some steel alloys using Geant4, MCNP, WinXCOM and experimental results,
agnostic X-rays, J. Appl. Polym. Sci. 127 (6) (2013) 49394946. Radiat. Phys. Chem. 106 (2015) 255260.
[7] J. Kim, D. Seo, B.C. Lee, Y.S. Seo, W.H. Miller, Nano-W dispersed gamma radiation [29] K.S. Mann, A. Rani, M.S. Heer, Shielding behaviors of some polymer and plastic
shielding materials, Adv. Eng. Mater. 16 (9) (2014) 10831089. materials for gamma-rays, Radiat. Phys. Chem. 106 (2015) 247254.
[8] W. Huang, W. Yang, Q. Ma, J. Wu, J. Fan, K. Zhang, Preparation and characterization [30] K.S. Krane, D. Halliday, Introductory Nuclear Physics, Wiley, New York, 1988.
of -ray radiation shielding PbWO4/EPDM composite, J. Radioanal. Nucl. Chem. 309 [31] J. Hubbell, Review of photon interaction cross section data in the medical and
(3) (2016) 10971103. biological context, Phys. Med. Biol. 44 (1) (1999) 122.
[9] X. Cao, X. Xue, T. Jiang, Z. Li, Y. Ding, Y. Li, H. Yang, Mechanical properties of [32] M.I. Sayyed, Bismuth modied shielding properties of zinc boro-tellurite glasses, J.
UHMWPE/Sm2O3 composite shielding material, J. Rare Earths 28 (2010) 482484. Alloys Compd. 688 (2016) 111117.
[10] T. Korkut, O. Gencel, E. Kam, W. Brostow, X-ray, gamma, and neutron radiation tests [33] V.P. Singh, N.M. Badiger, N. Kucuk, Determination of effective atomic numbers using
on epoxy-ferrochromium slag composites by experiments and Monte Carlo simula- different methods for some low-Z materials, J. Nucl. Ch. 2014 (2014) 17.
tions, Int. J. Polym. Anal. Charact. 18 (3) (2013) 224231. [34] M.L. Taylor, R.L. Smith, F. Dossing, R.D. Franich, Robust calculation of effective atomic
[11] H. Xiao, Y.G. Lu, M.H. Wang, X.Y. Qin, W.Z. Zhao, J. Luan, Effect of gamma-irradiation numbers: the Auto-Zeff software, Med. Phys. 39 (4) (2012) 17691778.
on the mechanical properties of polyacrylonitrile-based carbon ber, Carbon 52 [35] Y. Li, M. Li, Y. Gu, Z. Zhang, Numerical and experimental study on the effect of lay-up
(2013) 427439. type and structural elements on thickness uniformity of L-shaped laminates, Appl.
[12] Z.W. Xu, Y.D. Huang, C.Y. Min, L. Chen, L. Chen, Effect of -ray radiation on the Compos. Mater. 16 (2) (2009) 101115.
polyacrylonitrile based carbon bers, Radiat. Phys. Chem. 79 (8) (2010) 839843. [36] K. Zhang, Y. Gu, Z. Zhang, Effect of rapid curing process on the properties of carbon
[13] P. Wang, X. Tang, H. Chai, D. Chen, Y. Qiu, Design, fabrication, and properties of a ber/epoxy composite fabricated using vacuum assisted resin infusion molding,
continuous carbon-ber reinforced Sm2O3/polyimide gamma ray/neutron shielding Mater. Des. 54 (2014) 624631.
material, Fusion Eng. Des. 101 (2015) 218225. [37] Z.H. Wu, Experimental Methods in Nuclear Physics, Atomic Energy Press, Beijing,
[14] Z.X. Wu, J.W. Li, C.J. Huang, R.J. Huang, L.F. Li, Effect of gamma irradiation on the me- 1997.
chanical behavior, thermal properties and structure of epoxy/glass-ber composite, [38] A.A. Dalinkevich, K.Z. Gumargalieva, S.S. Marakhovsky, A.V. Soukhanov, Modern ba-
J. Nucl. Mater. 441 (1) (2013) 6772. salt fibrous materials and basalt fiber-based polymeric composites, J. Nat. Fibers 6
[15] Z.X. Wu, H. Zhang, H.H. Yang, X.X. Chu, L.F. Li, Novel radiation-resistant glass ber/ (3) (2009) 248271.
epoxy composite for cryogenic insulation system, J. Nucl. Mater. 403 (1) (2010)
117120.
[16] R. Li, Y.Z. Gu, Z.J. Yang, M. Li, S.K. Wang, Z.G. Zhang, Effect of gamma irradiation on
the properties of basalt ber reinforced epoxy resin matrix composite, J. Nucl.
Mater. 466 (2015) 100107.