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

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

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 661

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

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.
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 the graph. BK line at 104 eV was used for obtaining of Be spatial
some Fe/Be intermetallic phase. Mn and Al show a similar distribu- distribution. The OK spectrum is shown in the insert. Background
tion (Fig. 3c and d), whereas the Cr tends to form a core inside the in the was tted in the Be pre-edge region using power law
particle (Fig. 3e). Ti- and Si-rich phases are located on the right side I(E) = AE r, where E is the energy loss and A, rare tted constants.
or left side of the particle (Fig. 3f and g). In the Si map it is also vis- The correlation between the oxygen and the silicon map sug-
ible that Si forms a thin shell around the particle. Fig. 3h presents gests that this particle is enclosed by an SiO shell. Oxygen is not
an oxygen EELS map revealing that the edges of the beryllium present inside the impurity particles. As obvious from the beryl-
specimen and the edges of this particle are oxidized. The EELS lium EELS map (Fig. 3i), the particle additionally to the discussed
spectrum obtained from the edge of this beryllium particle, which above elements contains beryllium. Its intensity is remarkably
shows Be and O lines is imaged in Fig. 4. The original measured lower than intensity of surrounded matrix. These results suggest
spectrum in the range from 70 eV to 600 eV and the same spec- that complex particle is composed of several beryllium intermetal-
trum after background correction are shown in the main part of lic compounds.

3.2. Microstructure of irradiated Be

Analytical investigations of an area of a 28 lm long beryllium

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
Fig. 4. EELS spectrum obtained from the oxidized edge of beryllide particle showing material breaks along the impurity chains. Imaging of this ber
the BeK and OK lines. particle in an oxygen map (Fig. 6) reects the topography of the
 M. Klimenkov et al. / Journal of Nuclear Materials 455 (2014) 660664 663

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.

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
Fig. 6. High resolution oxygen map of brous beryllium particle investigated in beryllium with submicron grain size was not reported for pebbles
Fig. 5.
before, but has been observed for solid beryllium. Such beryllium,
similar to our nding, obviously shows a bimodal grain size distri-
beryllium surface which has been oxidized by contact with air. The bution. Chakin et al. [4] have demonstrated that grain size can
surface shows a clear brittle structure without any visible plastic range from sub-microns range to several hundred microns. Thor-
deformation. Analyzing the oxygen map, round oxide rings of ough comparison of these data with our results for pebbles is dif-
2030 nm in size can be found on the surface. One such ring is cult because the experimental information is not sufcient. In
marked by a square and represented in an enlarged manner in summary, these results demonstrate that grain sizes in beryllium
the insert. Several other rings are marked by arrows. In most cases, can vary for different production heats and different thermal treat-
such areas do not correlate with other elements. They presumably ments over a broad range.
mark location points of impurity precipitates that dropped out of The impurity particles detected in beryllium are mostly ran-
fracture surface. domly distributed in the matrix (Fig. 1d). However, in some cases
Bright eld TEM images of impurity particles after irradiation they are located along dislocation lines, forming chains of several
are shown in Fig. 7. These images are from the same particles microns in length (Fig. 2). The formation of such chains is not
shown in Fig. 5 that underwent analytical TEM investigation in observed in areas of nanostructured beryllium. Presumably the dis-
Fig. 5. The particle marked by number 1 (Fig. 7a) is also imaged locations are missing inside small grains or the grain boundaries
in Fig. 5a and marked there by number 1. The Fe-rich particle are more attractive nucleation sites for impurities. TEM analysis
marked by number 2 (Fig. 7b) is marked by number 2 in of beryllium powder pieces shows that impurity particles often
Fig. 5b. Small bubbles have formed inside the impurity particles are located on the fracture surfaces of the crushed particles. The
and are clearly visible in Fig. 7, especially for particle marked as chains of particles often wrap round the cracked beryllium
2. These bubbles were found in beryllide particles of Fe/Al/Mn pieces similar the area imaged in Fig. 5. This means that pebbles
composition (Fig. 7a) as well as in particles of Fe/Mn composition often break along such chains (Fig. 5). Considered statistically, such
(Fig. 7b). The size of the bubbles inside the particles ranges from surface location of impurity particles indicates that they lie on sur-
4 to 9 nm, which is signicantly smaller than that of the bubbles faces of preferred crack propagation. In some cases the surface
in beryllium [6]. Detailed investigation of these impurity particles depressions from impurity particles are oxidized and visible as a
in irradiated beryllium shows that the particles retain the ring in oxygen map (Fig. 6). In view of such oxygen-rings and the
mentioned core/shell structure, however the structure is less pro- distribution of precipitates, it may be concluded that beryllium
nounced than in the unirradiated Be. 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 4. Conclusion

impurities plays an important role in the fracture behavior of
beryllium. It can be supposed that local tensile stresses caused Extensive TEM investigations focused on distribution and com-
by swelling of impurity particles are the reason for such behavior. position of impurity particles in beryllium pebble were performed.
Micro-analytical characterization of impurity particles in beryl- The TEM imaging show that the grain size in beryllium pebbles
lium has not been the subject of many studies in the past. Most of ranges from several hundred nanometers to several tens of
the research more than 50 years ago was performed using X-ray microns. Investigation of impurity particles show that they contain
diffraction (XRD) that does not provide detailed analytical informa- of complex Fe/Cr/Al/Mn beryllide phases. These particles are
tion. The XRD investigations of extraction replicas of thermally mostly randomly distributed in beryllium matrix, however they
treated beryllium are presented in Ref. [11]. The investigation often decorate dislocation lines in micron-sized grains. The
proves the presence of particles with intermetallic Be5M and detected signicant swelling of these particles after neutron irradi-
Be13M compounds, where M can be Fe or Al. Generally, impurity ation can imply the differential stress in the matrix and contribute
segregation in beryllium differs between different production to the deterioration of the mechanical properties.
heats due to the signicant variation of impurities concentration.
In several research studies the presence of impurity particles in Acknowledgements
beryllium is mentioned without further analytical characterization
[9,10]. At the same time it is well known that mechanical proper- This work was supported by Fusion for Energy under the Grant
ties of Be are inuenced by impurity content [12,13]. Signicant Contract No. F4E-2009-GRT-030-03. The views and opinions
degradation of mechanical properties was observed in irradiated expressed herein reect only the authors views. Fusion for Energy
Be. The diffusion and precipitation on grain boundaries during is not liable for any use that may be made of the information
thermal treatment was suggested to be the main reason for the contained therein.
observed mechanical property degradation [14,15]. However as
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