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Materials Express
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Copyright 2011 by American Scientic Publishers
All rights reserved.
Printed in the United States of America
2158-5849/2011/1/273/006
doi:10.1166/mex.2011.1043
www.aspbs.com/mex
Enhanced X-Ray Shielding Effects of
Carbon Nanotubes
Toshihiko Fujimori
1
, Shuji Tsuruoka
1
, Bunshi Fugetsu
2
, Shigeo Maruyama
3
, Akihiko Tanioka
4
,
Mauricio Terrones
1, 5
, Mildred S. Dresselhaus
6
, Morinobu Endo
1
, and Katsumi Kaneko
1,
1
Research Center for Exotic Nanocarbons (JST), Shinshu University, Wakasato 4-17-1, Nagano 380-8553, Japan
2
Graduate School of Environmental Science, Hokkaido University, Sapporo, 060-0810 Japan
3
Department of Mechanical Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 133-8656, Japan
4
Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552, Japan
5
Department of Physics, Department of Materials Science and Engineering, and Materials Research Institute,
The Pennsylvania State University, 104 Davey Lab., University Park, Pennsylvania 16802, USA
6
Deapartment of Physics and Materials Science, Massachusetts Institute of Technology,
Cambridge, Massachusetts 02139-4307, USA
We report an explicit phenomenon related to the
X-ray attenuation inherent to carbon nanotubes
(CNTs). We observed that the mass attenuation
coefcient of CNTs was signicantly higher than
that observed for highly oriented pyrolytic graphite
(HOPG) and fullerenes (C
60
) by 2050%. The atten-
uation coefcient of CNTs increased by reducing
the sample thickness. This attenuation phenomenon
indicates the importance of the unique nanoscale
morphology of CNTs, which cannot be interpreted by
the already established X-ray absorption theory. In
order to demonstrate the effect of CNTs, we coated
a textile fabric with CNTs and found an enhanced
X-ray attenuation of 70% (textile thickness of 25 mm).
Therefore, CNT materials could now be used in the
fabrication of light-weight and efcient X-ray safety
equipment and devices.
Keywords: Carbon Nanotubes, X-Ray Attenuation
Coefcient, Cylindrical Tube-Like Structure.
1. INTRODUCTION
Carbon nanotubes (CNTs) could exhibit a high degree of
crystallinity and high electrical conductivity. The tubes

Author to whom correspondence should be addressed.

Email: kkaneko@shinshu-u.ac.jp
could be mainly classied into single-wall carbon nano-
tubes (SWCNTs) and multi-wall carbon nanotubes (MWC-
NTs). Interestingly, these tubular structures have been used
for electromagnetic shielding, particularly at high frequen-
cies in the GHz range. In this context, various types of
CNT composites have been fabricated by mixing the tubes
with polymer resins,
14
ceramics,
5
and metal powders.
6
These studies demonstrate that CNTs could exhibit novel
and outstanding electromagnetic effects. CNTs could con-
vert microwave energy into light
5
and/or heat in high
yields.
7
It is important to emphasize that CNTs possess
a unique structure consisting of cylindrical tubules that
could be nested (e.g., MWCNTs), and the interaction of
radiation with these tubules appears to be very differ-
ent when compared to interactions with planar or stacked
graphene sheets. The microwave absorption of CNTs is
usually discussed in terms of the electromagnetic wave
theory, as referred in theoretical approaches.
810
Although
an effective medium theory developed by Lagarkov and
Sarychev could describe the microwave absorption prop-
erties of CNT composites,
8
a clear explanation about the
enhanced microwave absorption properties of CNTs has
not been provided.
The optical properties of CNTs have been studied the-
oretically and experimentally. Grneis et al.
11
and Jiang
et al.
12
have developed the theory related to the optical
absorption of SWCNTs using band theory. These authors
showed an energy prole of CNTs describing the absorp-
tion dependence based on the graphene chiral angle. Yang
et al.
13
and Mizuno et al.
14
reported that aligned and
Mater. Express, Vol. 1, No. 4, 2011 273
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Materials Express
Enhanced X-Ray Shielding Effects of Carbon Nanotubes
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packed CNTs can perfectly absorb light with a normal
incidence of light with respect to the tubular axis. One
should note that the carbon atoms in tubular and chiral
concentric tubes are not periodic, and could exhibit dif-
ferent degrees of curvature. Therefore, one cannot use the
graphite (at) model to explain effects of incident photons
in CNTs. It is noteworthy that different types of nanoma-
terials have been actively studied using X-ray absorption
spectroscopy.
15, 16
These works reveal the presence of an
anomaly in X-ray absorption data, which arises from the
polarization function due to the electron population uc-
tuation. In addition, the recent study on Berry-phase tran-
sition in deformed crystals by Sawada et al.
17
indicates
the necessity of carrying out further fundamental studies
related to the interaction of X-rays with nanostructured
materials.
Here we report that CNTs could effectively attenu-
ate X-rays when compared to highly oriented pyrolytic
graphite (HOPG). Interestingly, we have found that not
only CNTs, but also CNT-coated fabrics efciently absorb
X-rays, and furthermore, their mass attenuation coef-
cients increased signicantly by reducing the thickness
of the compressed CNT specimens. Unfortunately, these
observations cannot be interpreted by the established X-ray
attenuation theory.
2. EXPERIMENTAL DETAILS
X-ray attenuation experiments using SWCNTs, MWC-
NTs, single-wall carbon nanohorns (SWCNHs), fullerenes
(C
60
), graphene oxide (GO), and a fabric-textile coated
with MWCNTs, were measured and compared with
HOPG. MWCNTs from Mitsui Co. & Ltd. (Mitsui
MWNT-7) and SWCNTs prepared at the University of
Tokyo were used. The SWCNHs sample was produced
by the NEC Corporation. Fullerenes were purchased from
the Wako Chemical Co. The MWCNT-coated textile (C-
Textile; 0.19 mm thick) was fabricated using polyester
bers coated with 8 wt% MWCNTs containing 2.5
wt% of TiO
2
. The bers were generally used for tex-
tile goods such as sports gears. Graphene oxide (GO)
was prepared from graphite by the Hummers method.
18
Samples other than HOPG, were compressed at 5
10
5
kN,m
2
(100(kN,14) 32 cm
2
) in order to form a
disc of 13 mm diameter and carry out the X-ray attenua-
tion measurements; the thickness of the pellets depended
on the carbon samples used. SWCNHs were compressed
at 3 10
5
kN,m
2
(50(kN,14) 32 cm
2
). Apparent den-
sities of the compressed samples were 1.19, 0.64, 0.36
and 1.470.02 g cm
3
for SWCNTs, SWCNH, MWNT-
7, and C
60
, respectively. We then used a monochromatic
incident X-ray beam of MoK
o
(\
0
=0.7107 , RINT TTR
II, Rigaku) in order to irradiate the samples mentioned
above, so that the attenuation was measured. Figure 1(a)
depicts a diagram explaining the orientation of the pel-
lets with respect to the incident irradiation. Here, I
0
and
Fig. 1. (a) Schematic diagram used to measure a specimen placed on
the target holder of the X-ray equipment, and (b) an experimental con-
guration used to generate the monochromatic X-ray beam (MoK
o
). The
sizes of Slit-1 and Slit-2 are 5 (width) 1 (height) mm and 20.8 mm
2
,
respectively. A scintillation counter is used for detecting intensities of the
X-ray.
I are X-ray intensities of the incident and transmitted
beams; I
0
was measured without a sample. In order to
generate the monochromatic incident X-ray beam, a non-
monochromatic X-ray was rst directed to a single crystal
of Ge(111) (Fig. 1(b)). The constructive diffraction from
the MoK
o
X-ray beam was obtained at 20 12.47 deg.
The scintillation counter was then adjusted and xed at this
angle. A tilt angle between the Ge surface and the incident
X-ray beam was then compensated by scanning the X-ray
source around 0 = 6.23 deg, in order to obtain the maxi-
mum beam intensity. The sizes of Slit-1 and Slit-2 were at
5 (width) 1 (height) mm
2
, and 20.8 mm
2
, respectively
(see Fig. 1(b)). The values of I and I
0
were averaged after
recording 100 measurement points. A statistical uctuation
of X-ray beam intensities occurred within 1%. We used
the well-known Beer-Lambert law to determine the mass
attenuation coefcient of the carbon specimens,
I
I
0
=e
(j,j)jx
(1)
where j, j and x are, respectively, the linear absorption
coefcient of material for X-ray absorption, the material
density, and the distance that the photon travels through
matter (i.e., the thickness of the absorbing layer). Here
we used the specimen density as the material density. The
term (j,j) is known as the mass attenuation coefcient
and has been widely used as an intrinsic value shown in
tables containing the X-ray mass attenuation coefcients.
19
3. RESULTS AND DISCUSSION
Strikingly, a signicant X-ray attenuation was observed
when using CNTs and the textile coated with CNT
(C-Textile) (see Fig. 2). The mass attenuation coefcients
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Enhanced X-Ray Shielding Effects of Carbon Nanotubes
Fujimori et al.
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of the SWCNTs, MWCNTs, SWCNHs, and the C-Textile
are much larger than that of HOPG (mass attenuation
coefcient: 0.576 to 0.581 cm
2
/g),
1921
which is depicted
by the horizontal dotted line in Figure 2. Our measured
mass attenuation coefcient for HOPG is very close to the
value reported in the literature. It is noteworthy that the
nanocarbons possessing nested cylindrical tubular struc-
tures reveal a higher X-ray attenuation coefcient when
compared to that of HOPG. We corrected the contribu-
tion of impurities within samples, by rst identifying the
type of impurities embedded in the materials using a
wavelength dispersive X-ray spectrometer (EPMA-1610,
Shimazu), followed by a calculation taking into account
the respective mass absorption coefcients.
11
In particu-
lar, we noted that SWCNTs contained 0.6, 0.4, 0.4, and
0.2 wt% of Fe, Co, Ni, and Cl, respectively. We also
noted that the mass attenuation coefcient of fullerenes
was almost equivalent to HOPG, and the cylindrically
rolled graphene structures (nanotubes) increased the X-ray
attenuation signicantly. This phenomenon does not fol-
low any conventional rule stating that the mass attenuation
coefcients are inherent to the type of elements contained
within the material. Figures 3(a) and (b) indicate the val-
ues of the mass attenuation coefcients as a function of
the sample thickness and the apparent densities, respec-
tively. The densities of MWCNTs show a clear dependence
of mass attenuation coefcient with respect to thickness,
whereas graphene oxides reveal a very subtle dependence
on the sample thickness. This observation conrms once
more that graphene oxides (exhibiting a at sheet struc-
ture) do not show any signicant thickness dependence,
and only cylindrical carbon nanostructures show such a
clear dependence. The latter demonstrates that cylindrical
carbon structures exhibit a unique dependence. Since the
Fig. 2. Mass attenuation coefcients of different carbon materials. The
incident X-ray beam was monochromatic MoK
o
(\ =0.7107 ) at 50 kV
and 10 mA. Width of the horizontal red belt shows the graphite mass
attenuation coefcient in the literature;
1921
those attenuation coefcients
for pure graphite are 0.566, 0.576 and 0.581 cm
2
g
1
.
Fig. 3. (a) Mass attenuation coefcients and (b) apparent densities of
various nanostructured carbon materials of different thicknesses. The
incident X-ray beam was non-monochromatic MoK
o
(\ = 0.7107 ) at
50 kV and 300 mA (RINT TTR II, Rigaku). HOPG has a xed value
and graphene oxide changed slightly with the thickness.
amount of impurities is low, we attribute the high mass
attenuation coefcients observed for CNTs to their nano-
structure and curved morphology.
We cannot explain the observed enhanced X-ray attenu-
ation properties of CNTs as yet. However, we need to take
into account that carbon atoms embedded in the hexagonal
tubular concentric tubes of different curvature, are not peri-
odic. This unique tubular structure of CNTs induces a sig-
nicant electron population uctuation across the carbon
tube wall. Such an electron population uctuation can lead
to an enhanced X-ray absorption caused by an increase
in the polarization factor.
11, 12
However, in the near future,
one would need to establish the experimental relationship
Mater. Express, Vol. 1, 2011 275
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(a) (b)
(c) (d)
Fig. 4. SEM images of: (a) the fabric laments coated with CNTs; (b) lower magnication of the fabric showing the ber yarns; (c) the ber cross
section before CNT coating, where 24 polyester laments were bundled, and (d) the ber cross section after coating with CNTs; CNT covered each
lament and the CNT layer thickness ranged between 100 and 500 nm.
between the X-ray attenuation property and the nano-
structure morphology from a theoretical standpoint.
The unusually high attenuation property of MWCNTs
could be efciently transferred to the C-Textile (Fig. 2).
This C-Textile constitutes a semi-commercial product
designed for planar heaters. However, we have found that
this C-Textile has an alternative potential application con-
sisting of the fabrication of X-ray shielding fabrics. In
particular, the polyester laments of C-Textile are uni-
formly coated by CNTs and a binder (Fig. 4). Figure 5
shows the percentage of attenuation versus the thickness of
several stacked textile sheets. The attenuation percentage
rapidly increases by increasing the fabric thickness, reach-
ing an attenuation percentage higher than 70% with 24 mm
thick lms. Figure 6 shows X-ray transparency images
and luminance distribution curves of the C-Textile and an
aluminum plate obtained using a Shimadzu Microfocus
X-Ray Testing System (SMX-1000). In these images, gray
values of 0 and 256 indicate blackness and whiteness,
respectively. The gray intensity is thus described from
0 through 256. Those values correspond to color pro-
les depicted on top of the luminance distribution curves
that are evaluated using the same dimensions of the
images depicted in Figures 6(a)(c). The aluminum plate
(0.31 mm thick) is the most transparent against X-ray
irradiation and reveals the sharp edges of the aluminum
plate. However, the edges of both textiles, with and with-
out MWCNTs, become diffused, indicating that both tex-
tiles are capable of attenuating X-ray more efciently.
The transparency difference between both textiles can be
Fig. 5. X-ray attenuation ratio as a function of the C-textile thickness.
The incident X-ray of MoK
o
was the same as the one shown in the
previous measurements. Individual C-textile sheets exhibited different
density values: sample 10.610 g/cm
3
, sample 20.610 g/cm
3
, sample
30.640 g/cm
3
, and sample 40.723 g/cm
3
.
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Enhanced X-Ray Shielding Effects of Carbon Nanotubes
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Fig. 6. X-ray transparency images and luminance distribution curves
using a Shimadzu microfocus X-Ray Testing System (SMX-1000).
(a) C-Textile coated with CNTs with a 3.8 mm thickness; (b) Textile
without CNTs and with a 5.0 mm thickness, and (c) an aluminum plate
with 0.31 mm thickness. The luminance distribution curves (a

)(c

) cor-
respond to (a)(c), respectively.
conrmed by evaluating the luminance distribution curves.
Larger gray values indicate a higher transparency, and
therefore the C-Textile is capable of shielding X-ray more
efciently than the textile without MWCNTs. For this rea-
son, we strongly believe that the C-Textile could be used
as a main component in safety instruments and fabrics
used for protection against X-ray radiation, and could be
used in nuclear power plants and when operating medical
equipment.
4. CONCLUSIONS
We have demonstrated the enhanced X-ray shielding of
CNTs. The mechanism for these observations is still
far from clear elucidation and it cannot be understood
by conventional X-ray attenuation theory. The unusu-
ally high shielding effect of CNTs is likely to origi-
nate from their unique cylindrical nano-morphology. These
observations are now opening new avenues for fabricat-
ing lightweight fabrics able to offer protection against
X-ray radiation and provided much lighter in-use-weight
in comparison with the current lead and/or the other heavy
metal base equipment. However, further fundamental
research is needed in order to elucidate the enhancement
mechanism of X-ray attenuation behind these reported
observations.
Acknowledgment: We thank the Rigaku Co. for tech-
nical assistance and NEC Corpolation for complementally
supplying us their SWCNHs. Also we thank Professor
Y. Natsume and Professor T. Fujikawa, Graduate School
of Science, Chiba University for their theoretical advices.
We thank Dr. H. Sakamoto for his experimental sup-
ports. Dr. M. Yudasaka offered SWCNH samples. Pro-
fessor Rodolfo Cruz-Silva kindly provided the graphene
oxide material for carrying out these measurements. TF,
ST, MT, ME and KK are supported by Exotic Nanocar-
bons, Japan Regional Innovation Strategy Program by the
Excellence, JST.
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