Journal of Nuclear Materials 455 (2014) 660664

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Journal of Nuclear Materials

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TEM study of impurity segregations in beryllium pebbles

M. Klimenkov a,, V. Chakin a, A. Moeslang a, R. Rolli b
a
Institute for Applied Materials Applied Materials Physics, Karlsruhe Institute of Technology, Hermann-von-Helmholz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
b
Institute for Applied Materials Materials and Biomechanics, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

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

Article history: Beryllium is planned to be used as a neutron multiplier in the Helium-cooled Pebble Bed European
Available online 28 August 2014 concept of a breeding blanket of demonstration power reactor DEMO. In order to evaluate the irradiation
performance, individual pebbles and constrained pebble beds were neutron-irradiated at temperatures
typical of fusion blankets. Beryllium pebbles 1 mm in diameter produced by the rotating electrode
method were subjected to a TEM study before and after irradiation at High Flux Reactor, Petten, Nether-
lands at 861 K. The grain size varied in a wide range from sub-micron size up to several tens of microm-
eters, which indicated formation bimodal grain size distribution. Based on the application of combined
electron energy loss spectroscopy and energy dispersive X-ray spectroscopy methods, we suggest that
impurity precipitates play an important role in controlling the mechanical properties of beryllium. The
impurity elements were present in beryllium at a sub-percent concentration form beryllide particles of
a complex (Fe/Al/Mn/Cr)B composition. These particles are often ordered along dislocations lines, form-
ing several micron-long chains. It can be suggested that fracture surfaces often extended along these
chains in irradiated material.
2014 Elsevier B.V. All rights reserved.

1. Introduction chemical composition and spatial distribution of impurity particles

It is suggested that beryllium will be used as a neutron multi-
plier material in the Helium-cooled Pebble Bed (HCPB) European
concept of a breeding blanket of demonstration power reactor
DEMO. In the neutron multiplier beryllium may take the form of
a bed of beryllium pebbles 1 mm in diameter [1]. During operation
of the fusion reactor, the beryllium pebbles will be exposed to
high-dose irradiation of 14 MeV neutrons, resulting in signicant
radiation damage. Radiation-induced helium and tritium produc-
tion in beryllium is calculated to be 25.700 appm and 640 appm,
respectively, corresponding to the expected end-of-life of the HCPB
blanket [2]. The maximum operation temperature that the present
blanket design can reach is 923 K.
Long-term irradiation tests in high-neutron-ux nuclear
research reactors yield information about the evolution of the
microstructure of beryllium pebbles under close-to-fusion condi-
tions (temperature, damage dose, helium and tritium production)
excluding 14 MeV neutrons which are not present in the neutron
spectrum of ssion reactors. High-temperature neutron irradiation
experiments of beryllium materials and subsequent investigations
of their microstructure by transmission electron microscopy (TEM)
have been carried out already [36]. This study focuses on analysis
Corresponding author. Tel.: +49 721 608 22903; fax: +49 721 608 24567.
E-mail address: michael.klimenkov@kit.edu (M. Klimenkov).
and their possible inuence on the formation of fracture surfaces
or crack propagation in beryllium.
Neutron radiation, in addition to helium and tritium produc-
tion, produces microstructural defects, such as vacancies or
interstitial defects, which result in the formation of dislocation
loops and He-lled bubbles or voids. Their characterization on
the nanoscale is important to understand changes of mechanical
and physical properties. This paper presents TEM investigations
of the microstructure of beryllium pebbles irradiated in the
High-Flux Reactor (HFR), Petten, within the HIDOBE-01 (HIgh DOse
Irradiation of BEryllium) experiment as well as of unirradiated
material [7].
Quantitative characterization of bubbles or voids allows for the
calculation of material swelling and, hence, its prediction. TEM has
been proven to be a powerful method for investigating such
defects. The combination of conventional imaging with electron
energy loss spectroscopy (EELS) on the nanoscale allows the
material to be characterized in detail. TEM studies of impurity dis-
tribution in beryllium samples in the form of pebbles are especially
important to the HCPB blanket concept.
The enhanced embrittlement of beryllium pebbles after irradia-
tion is often correlated with impurity concentration [8]. Commer-
cial beryllium contains numerous impurity elements, such as Fe,
Mn, Cr, and U, whose concentrations may vary for different
production heats [4,5,7]. Most publications about beryllium

http://dx.doi.org/10.1016/j.jnucmat.2014.08.030
0022-3115/ 2014 Elsevier B.V. All rights reserved.
 M. Klimenkov et al. / Journal of Nuclear Materials 455 (2014) 660664
properties and microstructure use the impurity content data from
data sheet of the manufacturer. The distribution of these elements
and their inuence on mechanical properties was not studied
properly in the past. There are few publications focusing on the
imaging of impurity particles in beryllium without any additional
analytical characterization [2,4]. The composition, morphology,
and distribution of precipitates remain unknown despite the fact
that impurities might play an important role in controlling
mechanical properties. This paper provides information on the
composition and spatial distribution of impurities. This informa-
tion allows suggestions concerning role of impurity particles in
the breaking mechanism of irradiated beryllium [7].
2. Experimental
The investigated beryllium pebbles have a diameter of 1 mm
and were fabricated by Nippon Gaishi Co., (NGK) Japan using the
rotating electrode method [9]. The beryllium pebbles contain the
following main impurities in wt.%: 0.36 BeO, 0.094 Fe, 0.048 Al,
0.029 Si, 0.024 Mg [9,10]. The HIDOBE-01 irradiation campaign at
HFR, Petten, started in June 2005 and was completed in October
2007 after 25 reactor cycles or 649 days at full reactor power
(>40 MW). The details of this irradiation program can be found in
Refs. [6,11]. The beryllium pebbles were crushed to nanosized
powder and investigated by means of TEM after deposition on a
carbon net. The details of preparation of a powder suitable for
TEM investigation can be found in Ref. [6].
The TEM investigations were performed using an FEI Tecnai 20
FEG microscope with an accelerating voltage of 200 kV, the scanning
unit for performing scanning TEM (STEM) equipped with a
high-angle annular dark eld (HAADF) detector, an energy-disper-
sive X-ray (EDX) detector for elemental analysis, and electron
energy loss spectroscopy (EELS) for the detection of light elements.
The analytical (EELS and EDX) investigations were performed in a
scanning TEM mode using a beam size of 1.5 nm.
3. Results and discussion
3.1. Microstructure of unirradiated Be
Scanning electron microscopy indicated that the grain size of
the pebbles was several tens of microns [8]. This result was also
conrmed by TEM investigations of irradiated beryllium powder
[6]. However, the pebbles in some areas were observed to have a
nano-grain structure. The dark eld TEM images of beryllium
particles with nano-grains are presented in Fig. 1. The grains vary
Fig. 1. Dark eld images of beryllium powder particle with nano-crystalline grain structure obtained using different reections (a and b), electron diffraction pattern (c) and
Fe elemental map (d) showing distribution of Fe precipitates obtained from the marked in parts (a and b) region.
661
in size from 50 to 300 nm and are often hexagonal in shape (Fig. 1a
and b). Dark eld imaging in TEM using different diffraction spots
yields grains with different crystallographic orientation with bright
or dark contrast. Rarely, the grains have low-angle boundaries with
each other. Several neighboring grains are imaged in the dark eld
micrograph and visible with a bright contrast in Fig. 1b. Fig. 1c
shows a diffraction ring pattern made of discrete spots. The pattern
demonstrates that beryllium in the areas of several microns, simi-
lar to the imaged in Fig. 1a, shows a slight texture. Diffraction pat-
terns from other thin areas of the same powder particle show that
grains are randomly oriented to each other. The detected slight
texture can be observed investigation areas of few microns. No
preferential wide ranging grain orientation or texture can be read
from the patterns. The pattern shows that beryllium pebbles have
a hexagonal structure with a lattice constant of a = 0.199 nm and
c = 0.359 nm.
Elemental EDX and EELS mapping were used to study the distri-
bution of impurity particles in the beryllium matrix. The analytical
results are presented in Fig. 1d and Figs. 2 and 3. The EDX Fe-Ka
line map of the area marked by a square in Fig. 1 is shown in
Fig. 1d. The randomly distributed precipitates of globular shape
show a complex composition of 52% Fe, 28% Al, 13% Mn, and 7%
Cr. The concentration of these elements can vary for different
impurity particles. Generally, particles of Fe or FeAl or FeAl
MnCr composition can be detected in the specimen. With the
exception of Fe, no random distribution of other elements was
detected. Detailed analysis of the Fe distribution presented in
Fig. 1d suggests low Fe enrichment on some grain boundaries.
These boundaries are marked by arrows in Fig. 1a and in the Fe
map (Fig. 1d). Fe enrichment is very weak, at the detection limit
of the EDX method, so that no further conclusions can be made.
In most cases, the impurity particles showed a random distribu-
tion, as obvious from Fig. 1d. Areas where particles were ordered
along some lines or on the grain boundaries were found very rarely
(Fig. 2). Fig. 2 presents the elemental analysis of precipitates in
such a one-dimensional chain. Analysis of images tilted with 15
degree conrms their one-dimensional alignment. The lines pre-
sumably were long dislocations which might have already existed
in beryllium during some fabrication stages and which served as
sites for preferable impurity precipitation. As evident, the particles
mostly have Fe/Al/Mn or Fe/Al/Mn/Cr composition (Fig. 2bd). The
presence of Cr was detected in two imaged particles only (Fig. 2e).
Fig. 3 presents the detailed EELS/EDX analysis of an impurity
particle located on the specimen edge. The particle of 70 nm in size
consists of complex Fe/Al/Mn/Cr/Ti beryllide composition. As it can
be seen, each element is enriched in separate areas of the particle.
Fe is present in all particles, but forms the phase on the left side,
662 M. Klimenkov et al. / Journal of Nuclear Materials 455 (2014) 660664

Fig. 2. HAADF images with revers of beryllium powder particle (a) and Fe, Mn, Al and Cr elemental maps of the marked area are imaged in parts (b, c, d) and (e) respectively.

Fig. 3. HAADF image of an impurity particle (a) and Fe, Mn, Al, Cr, Ti, Si, O and Be elemental maps are imaged in parts (bi) respectively. The maps of Fe, Mn, Al, Cr, Ti and Si
(parts (bg)) were obtained by EDS signal, whereas O and Be maps imaged in parts (h and i) were obtained using EELS.

where no other impurity elements are present. Possibly this is
some Fe/Be intermetallic phase. Mn and Al show a similar distribu-
tion (Fig. 3c and d), whereas the Cr tends to form a core inside the
particle (Fig. 3e). Ti- and Si-rich phases are located on the right side
or left side of the particle (Fig. 3f and g). In the Si map it is also vis-
ible that Si forms a thin shell around the particle. Fig. 3h presents
an oxygen EELS map revealing that the edges of the beryllium
specimen and the edges of this particle are oxidized. The EELS
spectrum obtained from the edge of this beryllium particle, which
shows Be and O lines is imaged in Fig. 4. The original measured
spectrum in the range from 70 eV to 600 eV and the same spec-
trum after background correction are shown in the main part of
the graph. BK line at 104 eV was used for obtaining of Be spatial
distribution. The OK spectrum is shown in the insert. Background
in the was tted in the Be pre-edge region using power law
I(E) = AE r, where E is the energy loss and A, rare tted constants.
The correlation between the oxygen and the silicon map sug-
gests that this particle is enclosed by an SiO shell. Oxygen is not
present inside the impurity particles. As obvious from the beryl-
lium EELS map (Fig. 3i), the particle additionally to the discussed
above elements contains beryllium. Its intensity is remarkably
lower than intensity of surrounded matrix. These results suggest
that complex particle is composed of several beryllium intermetal-
lic compounds.

3.2. Microstructure of irradiated Be

Analytical investigations of an area of a 28 lm long beryllium

Fig. 4. EELS spectrum obtained from the oxidized edge of beryllide particle showing
the BeK and OK lines.
particle are presented in Fig. 5. This particle is ber-shaped with
a length of 28 lm and width of 0.4 lm. Such beryllium particles
with an elongated shape can often be observed in the irradiated
specimens. Considering the chemical composition of impurities
shown in Fig. 3be, no signicant differences between impurity
particles in irradiated and unirradiated material were found. Most
particles are of Fe/Al/Mn/Cr composition. Several particles which
do not contain Al are marked in the Fe map (Fig. 5b). The morphol-
ogy of impurity chains shows that the particles are obviously
located on the fracture surfaces of Be. It can be assumed that the
material breaks along the impurity chains. Imaging of this ber
particle in an oxygen map (Fig. 6) reects the topography of the
 M. Klimenkov et al. / Journal of Nuclear Materials 455 (2014) 660664
Fig. 5. HAADF images of an part of a brous beryllium particle (a) and Fe, Mn, Al and Cr elemental maps are imaged in parts (be) respectively.
Fig. 6. High resolution oxygen map of brous beryllium particle investigated in
Fig. 5.
beryllium surface which has been oxidized by contact with air. The
surface shows a clear brittle structure without any visible plastic
deformation. Analyzing the oxygen map, round oxide rings of
2030 nm in size can be found on the surface. One such ring is
marked by a square and represented in an enlarged manner in
the insert. Several other rings are marked by arrows. In most cases,
such areas do not correlate with other elements. They presumably
mark location points of impurity precipitates that dropped out of
fracture surface.
Bright eld TEM images of impurity particles after irradiation
are shown in Fig. 7. These images are from the same particles
shown in Fig. 5 that underwent analytical TEM investigation in
Fig. 5. The particle marked by number 1 (Fig. 7a) is also imaged
in Fig. 5a and marked there by number 1. The Fe-rich particle
marked by number 2 (Fig. 7b) is marked by number 2 in
Fig. 5b. Small bubbles have formed inside the impurity particles
and are clearly visible in Fig. 7, especially for particle marked as
2. These bubbles were found in beryllide particles of Fe/Al/Mn
composition (Fig. 7a) as well as in particles of Fe/Mn composition
(Fig. 7b). The size of the bubbles inside the particles ranges from
4 to 9 nm, which is signicantly smaller than that of the bubbles
in beryllium [6]. Detailed investigation of these impurity particles
in irradiated beryllium shows that the particles retain the
mentioned core/shell structure, however the structure is less pro-
nounced than in the unirradiated Be.
663
3.3. Discussion
Characterization of powder particles prepared from beryllium
pebbles using TEM [6] and polished pebble surfaces using scanning
electron microscopy (SEM) [4,9] demonstrate, that beryllium
exhibits excessively large differences in grain size distributions.
According to SEM results the grain size can range from 10 to
500 lm. The TEM characterization of beryllium powder particles
shows, that they often are single crystals suggesting a grain size
greater than 10 lm in the original pebbles. However, in the present
work we found that beryllium in some areas exhibits a nanocrys-
talline structure with randomly oriented grains of several hundred
nanometers in the size (Fig. 1). The presence of nanostructured
beryllium with submicron grain size was not reported for pebbles
before, but has been observed for solid beryllium. Such beryllium,
similar to our nding, obviously shows a bimodal grain size distri-
bution. Chakin et al. [4] have demonstrated that grain size can
range from sub-microns range to several hundred microns. Thor-
ough comparison of these data with our results for pebbles is dif-
cult because the experimental information is not sufcient. In
summary, these results demonstrate that grain sizes in beryllium
can vary for different production heats and different thermal treat-
ments over a broad range.
The impurity particles detected in beryllium are mostly ran-
domly distributed in the matrix (Fig. 1d). However, in some cases
they are located along dislocation lines, forming chains of several
microns in length (Fig. 2). The formation of such chains is not
observed in areas of nanostructured beryllium. Presumably the dis-
locations are missing inside small grains or the grain boundaries
are more attractive nucleation sites for impurities. TEM analysis
of beryllium powder pieces shows that impurity particles often
are located on the fracture surfaces of the crushed particles. The
chains of particles often wrap round the cracked beryllium
pieces similar the area imaged in Fig. 5. This means that pebbles
often break along such chains (Fig. 5). Considered statistically, such
surface location of impurity particles indicates that they lie on sur-
faces of preferred crack propagation. In some cases the surface
depressions from impurity particles are oxidized and visible as a
ring in oxygen map (Fig. 6). In view of such oxygen-rings and the
distribution of precipitates, it may be concluded that beryllium
preferably breaks along surfaces or lines containing impurity
664 M. Klimenkov et al. / Journal of Nuclear Materials 455 (2014) 660664
Fig. 7. Bright eld TEM images of the area with impurity particles in beryllium investigated in Fig. 5.
particles. This is an indication that preferable precipitation of
impurities plays an important role in the fracture behavior of
beryllium. It can be supposed that local tensile stresses caused
by swelling of impurity particles are the reason for such behavior.
Micro-analytical characterization of impurity particles in beryl-
lium has not been the subject of many studies in the past. Most of
the research more than 50 years ago was performed using X-ray
diffraction (XRD) that does not provide detailed analytical informa-
tion. The XRD investigations of extraction replicas of thermally
treated beryllium are presented in Ref. [11]. The investigation
proves the presence of particles with intermetallic Be5M and
Be13M compounds, where M can be Fe or Al. Generally, impurity
segregation in beryllium differs between different production
heats due to the signicant variation of impurities concentration.
In several research studies the presence of impurity particles in
beryllium is mentioned without further analytical characterization
[9,10]. At the same time it is well known that mechanical proper-
ties of Be are inuenced by impurity content [12,13]. Signicant
degradation of mechanical properties was observed in irradiated
Be. The diffusion and precipitation on grain boundaries during
thermal treatment was suggested to be the main reason for the
observed mechanical property degradation [14,15]. However as
we have shown that beryllide particles have enhanced swelling
after neutron irradiation (Fig. 7). This differential swelling can
imply differential stresses and therefore facilitate the crack propa-
gation in beryllium along the chains of impurities.
The former results suggest that the precipitates in beryllium are
single phase particles [12]. The detailed analytical investigation of
individual particles shows that they usually contain of several
beryllide intermetallic phases (Fig. 3). The AlCrFe rich beryllide
phase is often found to be located inside the particle, whereas
the FeAl rich beryllide phase forms a shell on the outside of the
particles. The Si and Ti often form beryllide phases which do not
contain Fe and Cr. The quantitative elemental composition EDX
analysis shows that this particle contains Al 41%, Fe 27%, Cr 12%,
Mn 12%, Si 5% and Ti 3% distributed in 34 phases. This complex
structure of beryllide particles is retained after neutron irradiation
despite the formation of numerous bubbles and signicant swell-
ing. The analytical results presented here support the above men-
tioned microstructural explanations for radiation-induced
mechanical property degradation for beryllium.
4. Conclusion
Extensive TEM investigations focused on distribution and com-
position of impurity particles in beryllium pebble were performed.
The TEM imaging show that the grain size in beryllium pebbles
ranges from several hundred nanometers to several tens of
microns. Investigation of impurity particles show that they contain
of complex Fe/Cr/Al/Mn beryllide phases. These particles are
mostly randomly distributed in beryllium matrix, however they
often decorate dislocation lines in micron-sized grains. The
detected signicant swelling of these particles after neutron irradi-
ation can imply the differential stress in the matrix and contribute
to the deterioration of the mechanical properties.
Acknowledgements
This work was supported by Fusion for Energy under the Grant
Contract No. F4E-2009-GRT-030-03. The views and opinions
expressed herein reect only the authors views. Fusion for Energy
is not liable for any use that may be made of the information
contained therein.
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