http://dx.doi.org/10.5516/NET.06.2014.

015

PARTICLE SIZE-DEPENDENT PULVERIZATION OF B4C AND

GENERATION OF B4C/STS NANOPARTICLES USED FOR
NEUTRON ABSORBING COMPOSITES
JAEWOO KIM1,2*, JIHEON JUN3, and MIN-KU LEE1
1
Nuclear Materials Research Division
2
WCI Quantum Beam based Radiation Research Center, Korea Atomic Energy Research Institute
111-989 Daeduck-daero, Yuseong-gu, Daejeon-si 305-353, Republic of Korea
3
Department of Materials Science and Engineering, The Ohio State University
Columbus OH 43210, USA
*
Corresponding author. E-mail : kimj@kaeri.re.kr

Received February 17, 2014

Accepted for Publication June 02, 2014

Pulverization of two different sized micro-B4C particles (~10 m and ~150 m) was investigated using a STS based
high energy ball milling system. Shapes, generation of the impurities, and reduction of the particle size dependent on
milling time and initial particle size were investigated using various analytic tools including SEM-EDX, XRD, and
ICP-MS. Most of impurity was produced during the early stage of milling, and impurity content became independent
on the milling time after the saturation. The degree of particle size reduction was also dependent on the initial B4C size.
It was found that the STS nanoparticles produced from milling is strongly bounded with the B4C particles forming
the B4C/STS composite particles that can be used as a neutron absorbing nanocomposite. Based on the morphological
evolution of the milled particles, a schematic pulverization model for the B4C particles was constructed.
KEYWORDS : Boron Carbide, Neutron Absorber, Pulverization, Nanoparticles, Ceramic-metal Composite

1. INTRODUCTION probability between thermal neutrons and the B4C particles.

Boron carbide (B4C) is one of the most important and
widely used materials in nuclear science and engineering.
B4C is mainly used as a core element for the control rods
in nuclear reactor, and a neutron absorber/shield in spent
nuclear fuel storage and casks due to high thermal neutron
absorption cross-section (706 b, b ~10-24 cm2) of boron
and its mechanical stability [1,2]. While the applications
of nanotechnology are currently looking promising in
various engineering areas, it is relatively undeveloped in
nuclear engineering. In this regard, the use of nano-sized
B4C particles might be an interesting topic especially in
the enhancement of the material properties, as well as the
thermal neutron absorption ability of those systems. The
B4C size effect in a neutron absorber such as Boral has
been seriously investigated because of the criticality con-
cern caused by the neutron channeling effect when the
B4C particle used in Boral covers a large range from sev-
eral tens to hundreds of m [3,4]. Theoretical evaluation
also indicated that the ultrafine particles may affect the
neutron absorption of materials [5]. Nano-sized B4C par-
ticles increase the total particle surface area and enhance
the thermal neutron absorption by increasing the collision
Use of the nano-sized B4C particles as a reinforcement
agent for the polymer and metal composites was explored
to increase thermal neutron absorption ability as well as the
materials properties [6-10]. However, the synthesis and/
or preparation of the nano-B4C particles and the surface
treatment of the nano-B4C particles are both known to be
difficult tasks due to chemical and mechanical stability
of B4C [1].
Several methods including high temperature solid state
reaction of amorphous carbon and boron [11], low tem-
perature chemical reaction [12], laser ablation [13], thermal
and RF plasma [14,15], sol-gel method [16], and mecha-
nochemical and mechanical milling [17-20] to synthesize
and/or prepare the nano-B4C particles have been reported.
Among them, mechanical milling appears to be more effi-
cient in producing sub-micron B4C powder for the purpose
of neutron shielding than any other process, since it is simple
and readily applicable to mass production even though im-
purity generation and wide size distribution of the milled
particles can be major disadvantages of the milling pro-
cess. Especially, impurity generation is inevitable due to
high hardness of the B4C particles (Hv ~38 GPa) when they
are pulverized. In this investigation, however, we found

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KIM et al., Particle Size-dependent Pulverization of B4C and Generation of B4C/STS Nanoparticles used for Neutron Absorbing Composites

that B4C milling can produce the core-shell structured ce-
ramic (B4C) - metal (impurity) composite particles without
any additional agent, which can be useful for the neutron
absorbing metal composites [21-23]. The Fe-alloy coated
B4C composite particles may enhance the wettability of
B4C particles in the metal based neutron absorber com-
posites. We evaluated two different sized initial B4C parti-
cles, and the physical and chemical characteristics of pul-
verized B4C samples were investigated. One of the main
impurities for the STS milling system is iron (Fe), and
the degree of impurities should be dependent on the mill-
ing time and initial size of B4C under the milling energy.
To characterize the pulverized B4C nanoparticles, various
analytic means such as X-ray diffraction (XRD), scanning
electron microscope (SEM) coupled with energy disper-
sive X-ray spectroscopy (EDX), and inductively coupled
plasma mass spectrometer (ICP-MS) were used to verify
the core-shell structured B4C-STS composite particles.
Ball milling based pulverization scheme of B4C was also
presented with the stepwise evolution of the B4C mor-
phologies coated with the STS on the surface.
3. EXPERIMENTAL RESULTS
3.1 Morphological Changes of the Milled B4C Particles
Morphological changes of the crystalline structured
~10 m B4C (10-B4C) and ~150 m B4C (150-B4C) parti-
cles under various milling times and at an energy of 700
rpm were observed using the FE-SEM images as shown
in Fig. 1 and Fig. 2. Fig. 1(a) ~ (d) shows the SEM im-
ages of the initial 10-B4C, 2, 12, and 24 h milled B4C
particles, and Fig. 2(a) ~ (d) shows the SEM images of
the initial 150-B4C, 2, 12, and 24 h milled B4C particles,
respectively. As shown in the images, the sharp edges
of both the initial 10-B4C and 150-B4C particles disap-
peared after milling, and the shape of the particles was
changed to a rounded shape. Most of the milled parti-
cles appear to have an imperfect crystal structure, and the

2. EXPERIMENTAL

Two different sizes of the B4C particles (~150 m, Ko-

jundo Chem., Japan and ~10 m, Alfa Aesar, USA) were
pulverized using a planetary ball mill (Taemyung Inc.,
Republic of Korea). Stainless steel (STS) milling balls
with a 5 mm diameter and the STS milling vessels were
used. Here, STS are consisted of 17 ~ 19% of Cr and 8 ~
10% of Ni for the vessel and 13 ~ 15% of Cr and 1% of
Ni for the balls, and the balance with Fe (manufacturers
catalog). Ball to powder ratio and milling energy were set
at 10:1 and 700 rpm. To eliminate the temperature effect,
Fig. 1. SEM Images of Initial 10-B4C and 2, 12, and 24 h
the milling vessels were cooled using tap water during Milled 10-B4C Particles
milling. The duration of milling was set at 2 h, 12 h, and
24 h, respectively. After milling, the milled powder was
first collected manually, and traces of the samples in the
milling balls and vessels were washed out using ethanol
and dried in the furnace.
Field emission SEM coupled with EDX was used to
compare the morphology and the impurity of the B4C
particles depending on the milling time and initial parti-
cle size. The XRD patterns were obtained to evaluate the
crystallographic information as well as the types of the
generated impurities in the milled samples. Qualitative
and quantitative impurity analyses dependent on the initial
B4C particle size and the milling time were also carried
out. To analyze the metallic impurity using ICP-MS, the
milled powders were dissolved in 10 mol% diluted nitric
acid (HNO3), and a membrane with ~200 nm pores was
used to filter out the large B4C particles. Based on the
information obtained from these analyses, a schematic
milling model of B4C was suggested using the morpho- Fig. 2. SEM Images of Initial 150-B4C and 2, 12, and 24 h
logical evolution of the particles during milling. Milled 150-B4C Particles

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average particle size seems to be reduced as the milling 3.2 D

 egree of the Size Reduction of Milled 10-B4C
time increases, while the finer particles are found in large and 150-B4C
numbers in the milled 10-B4C samples than in the milled
The degree of size reduction of the B4C particle was
150-B4C samples. This indicates that the milling conditions
examined by measuring the mass fractions of the dispersed
in this experiment are able to pulverize the B4C particles
particles in the supernatant and the precipitate after they
even though the hardness of the STS is lower than that
were dispersed in ethanol using ultrasonic excitation
of B4C. This type of B4C pulverization was also reported
with a frequency of 20 kHz and a power of 45 W for 1
using STS and/or ZrO2 based milling media and vessels
h. The supernatant was separated by decanting the solu-
in the literatures [6, 20]. However, the generation of the
tion after 24 h of dispersion, and the dried samples were
impurity and the morphological change of the B4C parti-
weighed. Fig. 4 shows the mass fraction of the initial and
cles forming the ceramic-metal composite have not been
milled B4C samples remaining in the supernatants. This
considered up to now. In this investigation, it can be as-
may indicate the different degree of size reduction be-
sumed that the B4C particles covered with the impurity
tween 10-B4C and 150-B4C. For 10-B4C, the population
having an imperfect crystal structure could be generated
of the particles in the supernatant was increased to ~35
by milling pure B4C particles based on the evolution of
wt% for the first 2 h of milling from ~13.8 wt%, and it
the SEM morphologies.
was decreased and converged at ~27 wt% for 12 h and
Fig. 3 shows the SEM-EDX images for the 24 h milled
24 h milling. On the other hand, it was increased and
(a) 10-B4C particles and (b) 150-B4C particles. It was ob-
converged at ~17 wt% for 12 h and 24 h milling from
served that more STS impurities were generated in the
~1 wt% for initial 150-B4C. This convergence might be
milled 150-B4C particles than in the 10-B4C particles. For
the re-agglomeration of the fine particles during milling
10-B4C, the impurity in the spot s1 is 0.9 wt% of Fe, while
preventing the further pulverization [24]. Even though
O could be originated from the oxidation of the metallic
these measurements may not directly reflect the size dis-
impurities. On the other hand, the impurities in the spot
tribution of the milled B4C sample, it might be useful to
s2 are 14.5 wt% of Fe and 0.7 wt% of Ni. Although these
evaluate the degree of the fine particles and to optimize
concentrations can be slightly varied from spot to spot
the milling conditions. Here, the surface conditions for
and sample to sample, it is clear that the generation of the
all milled particles are assumed to be similar as they are
impurity for 10-B4C is much less than that of 150-B4C
bounded with the disorder structured STS nanoparticles.
due to a higher energy transfer between the 150-B4C par-
ticles and the milling balls than the 10-B4C. These clearly
show milling of the B4C particles can produce the B4C- 3.3 X-ray Diffraction Patterns of Milled B4C
STS composite particles without any additional agent. Pulverized B4C samples were analyzed using the vari-
ations of the x-ray diffraction peaks as shown in Fig. 5(a)
for 10-B4C and (b) for 150-B4C. The intensity of the peaks
for the milled B4C samples was greatly reduced compared to
the initial samples, while the peak decrease for the milled
150-B4C particles is more noticeable than the milled 10-

Fig. 4. Mass Fractions of Initial and Milled B4C Particles

Fig. 3. SEM-EDX Analysis for the Milled (a) 10-B4C Particles Remained in the Supernatant (after 24 h from the Ultrasonic
and (b) 150-B4C Particles Excitation)

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KIM et al., Particle Size-dependent Pulverization of B4C and Generation of B4C/STS Nanoparticles used for Neutron Absorbing Composites
B4C particles. Although the broadened width and the re-
duced intensity of the XRD peaks may present the par-
ticle size decrease in general, the decreased and broad
peak intensity in our case might be from the imperfect
structure of the STS nanoparticles bounded on the sur-
face of the B4C particles, not from the B4C particle itself.
Also the peak (110) for STS is shown for both, while the
peak for 150-B4C is much stronger than 10-B4C indi-
cating more STS impurity was produced in the milled
150-B4C samples. Here, the peak (110) belongs to Fe-Cr
based STS (JSPDS 34-0396) indicating that most impu-
rity might be produced from the balls. Also, the STS peak
was decreased as the milling time increases in Fig. 5(b).
This indicates that the crystallographic structure of STS
is disordered and led to the amorphous phase as the mill-
ing time increases. Amorphous STS combined with the
milled B4C particles interfere with the X-ray diffraction
patterns and decreases the peak intensity. This is the rea-
son why the peaks for milled 150-B4C particles are lower
than the milled 10-B4C particles. This was also confirmed
by the quantitative measurements using ICP-MS.
Fig. 5. X-ray Diffraction Patterns for Milling Time Dependent
Initial and Milled (a) 10-B4C and (b) 150-B4C particles
678
3.4 A
 nalyses of the Nitric Acid Treated Milled B4C
Samples
After the milled B4C particles were dissolved in 10
mol% diluted nitric acid (HNO3), a membrane with ~200
nm pores was used to filter out the large B4C particles,
and the mass fractions of the milled B4C particles larger
than ~200 nm were measured. The X-ray diffraction pat-
terns of the 12 h milled 150-B4C particles before and after
the nitric acid treatment were compared in Fig. 6. As it can
be expected, the X-ray diffraction patterns for the nitric
acid treated particles were restored. The restoration of the
B4C peaks indicates that most of the STS nanoparticles
coated on the surface of the B4C particles were dissolved,
while some STS remnants are still bounded on the surface
of the B4C particles according to the remained peak. After
the membrane filtered B4C particles were dried, the SEM
images were also obtained to compare the morphologies
with the untreated milled B4C particles as shown in Fig. 7.
For both 10-B4C and 150-B4C particles, the sharp edges
of the particles were restored similarly with the XRD patterns.
Also, the impurity dissolved in nitric acid was analyzed
using ICP-MS. Table 1 shows the elemental weight con-
centrations of the generated impurities contained in the
milled B4C samples. The impurity generation was more
serious for 150-B4C (23 wt% for 12 h milling and 24.6
wt% for 24 milling) than 10-B4C (5.4 wt% for 12 h milling
and 4.1 wt% for 24 h milling) as expected, while it appears
independent from the milling time. Most of the impurity
is Fe with some traces of Cr and Ni. The fractions of the
B4C particles less than ~200 nm were greatly increased
from 17.2 wt% to 42.0 wt% for 10-B4C and from 2.4 wt%
to 23.7 wt% for 150 B4C, as the milling time increased
from 12 h to 24 h, respectively. This indicates that the
fractions of B4C less than ~200 nm are dependent on both
the initial size of B4C and the milling time. However, the
fractions of the B4C particles larger than ~200 nm are
Fig. 6. X-ray Diffraction Patterns of 12 h Milled 150-B4C
before and after Nitric Acid Treatment
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 KIM et al., Particle Size-dependent Pulverization of B4C and Generation of B4C/STS Nanoparticles used for Neutron Absorbing Composites

independent from the initial size of B4C, while dependent
only on the milling time. Consequently, we can assume
that use of 10-B4C might be more beneficial to produce
the B4C/STS composite nanoparticles than 150-B4C.
Fig. 7. SEM Images of the 24 h Milled (a) 10-B4C and (b) 150-
B4C Particles after the Nitric Acid Treatment
3.5 B4C Size Dependent Pulverization Scheme
Based on the analyses on the B4C size reduction and the
impurity generation, we present a particle size depend-
ent pulverization scheme. Fig. 8 illustrates the suggested
stepwise pulverization of the B4C particles. We assumed
two pulverization processes, main pulverization and sub-
pulverization, while the former is more probable for 150
B4C and the latter is more probable for 10-B4C. For 150-
B4C, the main pulverization process might be dominant
and it is the reason for the small faction of the B4C par-
ticles less than ~200 nm after milling. The bigger parti-
cles can be divided into several smaller particles by the
main pulverization, while the sharp edges of the smaller
particles can be further pulverized into nano-sized parti-
cles by the sub-pulverization process. Impurity generation
could be from the main pulverization due to higher energy
transfer between the balls and the particles. During the
pulverization process, the STS nanoparticles from the
milling media can be bounded to, and/or interdiffused in,
the pulverized particles. As the number of the B4C par-
ticles bounded with the STS nanoparticles increases, the
generation of the STS impurity and further pulverization
will be reduced. This might be the reason why the impurity
concentration was barely dependent on the milling time,
while strongly dependent on the initial size of the particles.
Generation of the metallic impurity known as a disadvan-
tage for a milling process may act as an advantage produc-
ing the B4C-STS composite particles. This pulverization

Table 1. Mass Fractions of the Impurities in the Milled B4C Powders Generated after Milling based on the ICP-MS Measurements

Milling time B4C > 200 nm B4C < 200 nm Total B4C Fe Cr Ni Impurity
Type
(h) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%)

12 77.4 17.2 94.6 4.9 0.4 0.1 5.4

10-B4C
24 53.9 42.0 95.9 3.7 0.3 0.1 4.1
12 74.6 2.4 77.0 21.0 1.7 0.3 23.0
150-B4C
24 51.8 23.7 75.4 21.9 2.1 0.6 24.6

Fig. 8. Schematic Model for Pulverization of B4C

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KIM et al., Particle Size-dependent Pulverization of B4C and Generation of B4C/STS Nanoparticles used for Neutron Absorbing Composites
scheme may offer some practical aspects of milling for
very abrasive material such as B4C and useful to optimize
the ball milling process.
4. CONCLUSION
B4C is one of the most important materials in nuclear
engineering due to its superior thermal neutron absorp-
tion ability as well as the mechanical and chemical stabil-
ity. Furthermore, use of nano-sized B4C may offer some
engineering benefits in the enhancement of thermal neu-
tron absorption efficiency and the materials properties.
However, both the preparation of nano-size B4C particles
and their surface treatments are not well established yet.
In this investigation, we explored the pulverization of
B4C dependent on the initial particle size and the milling
time using a STS milling system. Most of impurity was
produced during the early stage of milling, and impurity
content became independent from milling time after the
saturation. Also, the generated STS nanoparticles could
be bounded to the surface of the B4C particles forming
the B4C/STS composites particles. The B4C size depend-
ent pulverization scheme was constructed based on the
morphological evolution of the milled particles and phys-
ical/chemical characteristics of the generated impurities.
We found that use of 10-B4C as an initial material for pul-
verization might be more beneficial to produce the B4C/
STS composite nanoparticles than 150-B4C.
ACKNOWLEDGEMENT
This study was performed under the financial support
partly from the Internal Research Program of Korea Atom-
ic Energy Research Institute and partly from the World
Class Institute (WCI) Program of the National Research
Foundation of Korea (NRF) funded by the Ministry of
Science, ICT and Future Planning, Republic of Korea.
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