Journal of Nuclear Materials xxx (2010) xxxxxx

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Journal of Nuclear Materials

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Pores and cracks in highly neutron irradiated beryllium

V. Chakin a,, R. Rolli b, H.-C. Schneider b, A. Moeslang a, P. Kurinskiy a, W. Van Renterghem c
a

Karlsruhe Institute of Technology, IMF I, P.O. Box 3640, 76021 Karlsruhe, Germany Karlsruhe Institute of Technology, IMF II, P.O. Box 3640, 76021 Karlsruhe, Germany c SCKCEN, Boeretang 200, B-2400 Mol, Belgium
b

a r t i c l e

i n f o

a b s t r a c t
Beryllium, irradiated in the SM and BR2 research nuclear reactors at 323343 K up to neutron uences of (0.414.4) 1022 cm2 (E > 0.1 MeV), was investigated. The dependences of beryllium swelling, brittle strength and microhardness on fast neutron uence are presented. Three intervals can be outlined where the swelling has the various rates of increase with the growth of the neutron uence that is connected with accumulation of radiogenic helium in beryllium and evolution of grain boundaries pores to cracks with the formation of a volume-connected network of cracks. The key points for the crack formation and propagation in beryllium under irradiation are the presence of beryllium oxide particles on boundaries and compression of the hexagonal grains along parameter c owing to radiation growth. The annealing at 1123 K for 5 h results in an increase of the helium amount on grain boundaries and an evolution of the pores to gas bubbles. 2010 Elsevier B.V. All rights reserved.

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1. Introduction At present beryllium is widely used in research nuclear reactors as a neutron reector and moderator [1]. Despite the operational successful experience with beryllium blocks under irradiation, there are some problems related to radiation damage [2]. The neutron irradiation induces the formation of helium atoms in a beryllium microstructure that causes dimensional changes such as swelling and radiation growth [3], and the degradation of mechanical properties. The radiation embrittlement is accompanied by formation of cracks, and leads, nally, to the failure of beryllium blocks [4]. The nature of a strong degradation of beryllium properties under neutron irradiation regards, rstly, to an anisotropy of the hexagonal closed-packed (hcp) lattice, secondly, to manufacturing methods by powder metallurgy that leads to a relative weakness of grain boundaries comparing to cast materials. Several studies have already been performed aiming to understand the roles of radiogenic helium, crystal anisotropy and grain boundary properties on mechanisms of beryllium radiation damage from low temperature neutron irradiation [57]. However, up until now, the clear understanding of these mechanisms does not exist. In this paper, the investigation of swelling and embrittlement of beryllium irradiated in the SM and BR2 research reactors at low temperatures up to high neutron uences is extended, with an accent on the role of grain boundaries towards these radiation effects.
Corresponding author. Tel.: +49 7247 82 3639; fax: +49 7247 82 4567.
E-mail addresses: vladimir.chakin@imf.fzk.de, vladimir.chakin@kit.edu (V. Chakin), rolf.rolli@imf.fzk.de (R. Rolli), wvrenter@sckcen.be (W.V. Renterghem). 0022-3115/$ - see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.jnucmat.2010.11.098

2. Experimental 2.1. The samples The chemical composition of the investigated beryllium grades is presented in Table 1. The beryllium grades were manufactured by similar methods and have the chemical compositions close to each other; therefore, comparative investigations could be performed. In this work the samples of the TE-56 beryllium grade irradiated in the SM research reactor, located at Dimitrovgrad, Russia, at 343 K up to neutron uences of (0.414.4) 1022 cm2 (E > 0.1 MeV). These samples were manufactured by hot extrusion (HE) of beryllium powder after preliminary hot-pressing. In addition, there were used fragments of the second beryllium matrix (19801995) from the BR2 materials testing reactor, located at Mol, Belgium, that were irradiated during operation at 323 K up to neutron uence of 4.67 1022 cm2 (E > 1 MeV) [8] that means a value of %9.3 1022 cm2 (E > 0.1 MeV). The irradiation parameters are given in Table 2. The original material of the matrix was the S-200-E beryllium grade manufactured by vacuum hot-pressing (VHP) of beryllium powder. For the investigation in initial state, the S-200F beryllium grade having the chemical composition close to S-200-E and also manufactured by VHP was used. The irradiated matrix fragments from the S-200-E beryllium grade were investigated in an as-received state after annealing at 1123 K for 5 h in vacuum (1.33 102 Pa). The TE-56 beryllium grade irradiated in the SM reactor at 343 K up to neutron uence of 5.7 1022 cm2 (E > 0.1 MeV) was also investigated after vacuum annealing at 1073 K for 1 h.

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2 Table 1 Chemical composition in wt.% of beryllium grades. Grade TE-56 S-200-E S-200-F
a

V. Chakin et al. / Journal of Nuclear Materials xxx (2010) xxxxxx

Be 98.6 >98 98.7

BeO 1.48 <2.0 1.18

C 0.08 <0.15 0.037

Mg No data <0.08 0.0015

Al 0.026 <0.15 0.043

Si 0.016 <0.08 0.0275

Fe 0.17 <0.18 0.116

Other
a

<0.04 Each
a

Balance.

Table 2 Irradiation parameters for beryllium grades. Grade TE-56 S-200-E Temperature (K) 343 323 Neutron uence,1022 (cm2) E > 0.1 MeV 0.414.4 %9.3 Damage (dpa) 2.280 57
4

He accumulation (appm)

80029,000 22,000

2.2. Examination methods The results on swelling were obtained by measuring of hydrostatic density and sizes of beryllium samples before and after irradiation and comparing these values. The measurement error for the hydrostatic method was 0.2%, and the error for the geometrical was 0.1% [9]. The samples of the TE-56 grade for the tensile tests were in a form of cylindrical dumbbells with a gauge section having diameter of 3 mm and a length of 10 mm. The mechanical tests were carried out at room temperature in air with a strain rate of 1 mm min1. All irradiated samples have shown absolutely brittle type of failure. Therefore, the measured parameter was brittle strength. The error for the strength measurements was 3%. The helium concentration in irradiated beryllium was measured by a mass-spectrometer using the isotope-dilution method [10]. The microstructure examination was carried out by optical microscope Olympus GX51. The microhardness measurements were performed by microhardness system MHT-10 made by Paar. The error for the microhardness measurements was 3%, The Scanning Electron Microscopy (SEM) examination was performed using Cam Scan 44 (Olympus) microscope (40 kV). 3. Results 3.1. Swelling and tensile properties Fig. 1 shows the dependence of beryllium swelling on fast neutron uence measured by density and dimensional changes. Three

uence intervals can be outlined where the swelling has the different rates of increase with the increase of the neutron uence. The rst interval is from zero to (34) 1022 cm2 where the rate of the swelling increase has a maximal value, the second interval is from 4 1022 cm2 to (910) 1022 cm2 where it is slowed down, the third interval is from 10 1022 cm2 to (1415) 1022 cm2 where the rate of the swelling increases again with a growth of the neutron uence. In all investigated neutron uence intervals, the swelling values measured by hydrostatic methods are always higher than measured by geometrical method. This can be explained by the inuence of relief at the surface which differs by wettability in a working liquid that leads some decrease of density of the measured sample. The neutron irradiation leads to a strong drop of strength of beryllium in an interval from zero up to a neutron uence of (2 4) 1022 cm2 (see Fig. 2). In an interval from 4 1022 cm2 up to (710) 1022 cm2 the brittle strength has approximately the same value around 150 MPa. The brittle strength decreases again from a uence of about (810) 1022 cm2 to a higher neutron uences. 3.2. Microhardness and helium accumulation From zero to (46) 1022 cm2 the microhardness increases quickly with a growth of neutron uence (see Fig. 3). But from the value of 6 1022 cm2 the microhardness increase becomes less signicant. The helium accumulation depends on the neutron uence similarly to the microhardness (Fig. 4). Up to 6 1022 cm2, the linear

3.0 2.5

density geometrical

500

Brittle strength (MPa)

400

Swelling (%)

2.0 1.5 1.0 0.5 0.0

300

200

100

0
0 2 4 6 8 10
-22

12
-2

14

16

-2

10
-22 -2

12

14

16

Neutron fluence, 10

(cm )

Neutron fluence, x10

(cm )

Fig. 1. Swelling versus neutron uence (E > 0.1 MeV) for beryllium irradiated at 343 K.

Fig. 2. Brittle strength versus neutron uence (E > 0.1 MeV) for beryllium irradiated at 343 K.

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V. Chakin et al. / Journal of Nuclear Materials xxx (2010) xxxxxx

9000 8000

Microhardness (MPa)

7000 6000 5000 4000 3000 2000 -2 0 2 4 6 8 10

-22 -2

accumulation rate can be determined by a partial release of helium from beryllium at maximum neutron uences of (1214) 1022 cm2, despite the low temperature of the irradiation. The correlation of the dependences of microhardness and helium accumulation on the neutron uence conrms the dening role of radiogenic helium as a factor for hardening of beryllium during neutron irradiation [11,12]. 3.3. Pores and cracks evolution Fig. 5 shows optical micrographs of the S-200-F beryllium grade before irradiation (Fig. 5a) and S-200-E after irradiation (Fig. 5b). In the initial state, pores of large sizes in the microstructure are absent. The irradiation leads to a formation of pores with sizes which are comparable to the grain sizes (1050 lm). Inside the large pores the second phase particles are sometimes visible. Beryllium oxide (BeO) is present in the investigated beryllium with a fraction of 2% (see Table 1). The pores are located at the grain boundaries or directly close (in vicinity) to them. In the irradiated, beryllium the cracks are observed along the consistently located pores, however, they do not always follow the grain boundaries. Sometimes, the crack passes through a grain body forming some bends. From Scanning Electron Microscope (SEM) images of the cracks in irradiated beryllium (Fig. 6), it was observed that, as a rule, the pores located on cracks have their forms extended along the cracks (Fig. 6a). A pore in a cross section looks like a polygon at an acute angle from a direction of crack propagation (Fig. 6b). The magnication on the SEM picture does not allow to see a beryllium oxide particle in the pore because, according to the results of TEM examination, the sizes of small particles located on the grain boundaries in beryllium vary from say 30500 nm [13]. The surface of the beryllium matrix fragment formed by means of a shock inuence from a manipulator was investigated (Fig 7). This mechanical inuence led to a fragile failure of the fragment (Fig. 7a and b). The type of the fracture is mixed and it occurs both inside the grains and on the grain boundaries. There are some visible pores of a few micrometers (Fig. 7c), and also beryllium oxide particles up to 1 lm (Fig. 7d). An annealing at 1123 K for 5 h leads to a substantial growth of quantity of pores with a large size in the microstructure of irradiated beryllium (Fig. 8). The pores are mainly located along the grain boundaries forming extended chains (Fig. 8a). As a rule, the pores have an irregular form with a facet (Fig. 8b). In [11,12,14] the inuence of annealing at temperatures of 7731473 K for 12106 h on a microstructure of beryllium irradiated at 323 and 343 K was investigated. In these studies the opinion was presented that the radiogenic helium plays the dominant role in processes of

12

14

16

Neutron fluence, x10

(cm )

Fig. 3. Microhardness versus neutron uence (E > 0.1 MeV) for beryllium irradiated at 343 K.

dependence of helium accumulation on the neutron uence takes place, but at uences above than 6 1022 cm2 the helium accumulation decelerates. However, theoretical calculations predict a linear dependence of the helium accumulation in beryllium [10]. Therefore, the experimentally measured slowing down of the

20000 18000

He accumulation (appm)
4

16000 14000 12000 10000 8000 6000 4000 2000 0 0 2 4 6 8

-22

10

12
-2

14

Neutron fluence, x10

(cm )

Fig. 4. Accumulation of 4He in beryllium irradiated at 343 K versus neutron uence (E > 0.1 MeV).

Fig. 5. Optical images of the beryllium samples in an initial state (a) and after irradiation at 323 K (b). The crack runs along the pores on the grain boundaries and in the grain body.

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beryllium microstructure evolution at a neutron irradiation, which redistribution at high-temperature annealing leads to formation of gas bubbles in a grain body and on grain boundaries. The process of redistribution of helium atoms runs quite quickly due to diffusion and nishes within the rst hours of an annealing. The large swelling of the irradiated and annealed beryllium was explained by the growth and the coalescence of already formed bubbles and by the formation of a large quantity of new gas bubbles. 4. Discussion It is known that the main reason for swelling and changes in the mechanical properties for irradiated beryllium is the formation of radiogenic helium. However, the mechanisms of these effects are

not clear up to now and demand more precise understanding. For the analysis of a grain boundary state in beryllium we will take the approach stated in [1517]. An isolated extended pore is located on a boundary of two grains disoriented by an angle a (Fig. 9). There is a at particle of BeO inside the pore and a crack is initiated by the pore. The beginning of the crack is located at the point A. A necessary condition for the crack propagation is the presence of a strength r applied at the point A perpendicularly to the boundary. In a general case

r rgrow rgas

rgrow is the strength caused by compression of the grains along parameter c owing to radiation growth [3]; rgas is the strength caused by internal gas pressure in the pore.

Fig. 6. SEM images of the beryllium sample irradiated at 323 K. The pores have an elongated shape in the direction of the crack propagation (a). The cross section of the pore is a polygon with acute corners (b).

Fig. 7. Fracture surface of the beryllium sample irradiated at 323 K: (a) general view of the fracture; (b) mixed character of the failure; the cleavage runs along the grain boundaries and in the body of grain; (c) large pores have been observed along the boundaries; (d) BeO particles with the sizes up to 1 lm are seen on the boundaries.

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Fig. 8. SEM images of the beryllium sample irradiated at 323 K and annealed at 1123 K for 5 h: (a) as-received after irradiation; (b) with an additional annealing at 1123 K for 5 h.

The TEM examination of beryllium irradiated at 343 K shows [14] that the formation of helium bubbles does not occur and the reason of that is the low diffusion mobility of helium atoms at low temperatures. Therefore, it is logical to assume that in (1) rgas is close to zero, and the growth of the crack along the grain boundary in this case is dened by rgrow only. From [3] it follows that the reduction of the parameter c reaches 0.0025 nm. Using the Hookes law for an estimation of the strains caused by this deformation, and the Youngs modulus for beryllium (3 104 kg cm2) [5], r = rgrow = 42 MPa received. The strength r is related to a critical crack size L according to the Grifth equation

cracks. The fracture surface of the TE-56 beryllium grade irradiated in the SM reactor at 343 K up to neutron uence of 5.7 1022 cm2 and annealed at 1073 K for 1 h is presented in Fig. 10. The type of the failure is typically intergranular, and the destruction occurs on grain boundary gas bubbles.

grain 1

BeO particle grain boundary

 1=2 2Ec pL

Using the surface tension coefcient c = 1.4 J cm2 for beryllium by a calculation with (2) L = 15 mm received. It is known from [18] that a critical crack size for beryllium makes 0.21 mm. Thus, L for a homogeneous polycrystalline beryllium is very large. However, on the grain boundaries there are BeO particles which are located on much smaller distances from each other 110 lm (Fig. 5b). Therefore, a crack extending in a direction of the minimum resistance connects the pores located consistently along the grain boundary without achieving the values of the critical size. Besides, by favorable mutual orientation of two grains, the crack can leave the grain boundary and extend on a grain body along basal plane   (0 0 0 1), second-order prismatic f1 1 2 0g planes, and f1 0 1 2g twin boundaries [19]. This leads to the mixed type of the failure of irradiated beryllium (Fig. 7b). Another situation occurs at a high-temperature annealing of beryllium irradiated at a low temperature when the diffusion mobility of helium atoms becomes much higher, and the gas pressure inside the pore cannot be neglected. After transformation of the equation from [16] it is received for the pressure caused by a gas in the pore

crack direction

grain 2

pore

Fig. 9. The schematic view of isolated elongated pore located on the boundary between two grains with different orientation. There is a BeO particle inside the pore.

rgas

r 8K 9p2 L

pEc L is the length of a pore along a grain boundary; K 1m2 the known material constant; c the coefcient of surface tension; E is the Youngs modulus. Substituting in (3) the constants for beryllium specied above, and also value L = 20.7 lm directly measured in Fig. 6b, rgas = 758 MPa received that is essentially higher than rgrow for irradiated Be without annealing. It means that after high-temperature annealing the majority of helium atoms moves to grain boundaries where gas plays a key role to the size increase of the pores, evaluating to gas bubbles, and leads, accordingly, to the propagation of

Fig. 10. SEM image of the beryllium sample irradiated at 343 K and annealed at 1073 K for 1 h. The failure of the sample occurs on gas bubbles located along the boundaries.

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The evolution of the swelling and mechanical characteristics of beryllium versus neutron uence can be explained on the basis of stated above (Figs. 13) as follows. According to [6], so-called solid swelling of beryllium occurs up to neutron uence of (34) 1022 cm2 which is caused by a distortion of the beryllium lattice owing to the accumulation of radiogenic helium and the absence of signicant diffusion of the gas atoms (Fig. 1). From 4 1022 cm2 to (910) 1022 cm2 the swelling increase slows down, which can be related to the beginning of a sufcient transfer of helium to the grain boundary pores. At this moment, the sizes of pores were already essentially enlarged owing to anisotropic changes of sizes of separate grains. At the same time, the growth of cracks inuences the mechanism of connection of the pores between each other. By neutron uences exceeding of 10 1022 cm2 the growth of cracks along the grain boundaries becomes avalanche-like, which leads to the accelerated swelling. Thus, the further increase in a volume of the beryllium sample occurs already by means of the formation of the volume-connected network of cracks. The behaviour of the brittle strength versus the neutron uence (Fig. 2) correlates with the swelling curves. The maximal drop of the brittle strength occurs up to the uence of (24) 1022 cm2 that coincides with the interval of the solid swelling of beryllium. The stabilization of the brittle strength level takes place in an interval from 4 1022 cm2 up to (710) 1022 cm2 when some sufcient part of helium comes to grain boundaries. Only from (9 10) 1022 cm2 does the further decrease in the brittle strength caused by the formation of a network of cracks take place. 5. Conclusion TE-56 grade beryllium samples irradiated in the SM reactor at 343 K at neutron uences from 0.4 1022 to 14.4 1022 cm2 (E > 0.1 MeV) were investigated. In addition, fragments of beryllium matrix from the S-200-E beryllium grade from the BR2 reactor irradiated at 323 K up to neutron uence of about 9.3 1022 cm2 (E > 0.1 MeV) in an as-received state after irradiation and after additional annealing at 1123 K for 5 h were also used in this work. From the observed changes of swelling, brittle strength and microhardness of beryllium on the fast neutron uence, it is possible to allocate the stages differing in the variation of properties with the neutron uence. The nature of these stages is related to the accumulation of radiogenic helium in beryllium at the neutron irradiation that leads to the increase in the size and quantity of the pores located on grain boundaries. This yields anisotropic changes of the grain size and the corresponding increase of the strains around the boundaries. The grain boundary pores are the

nucleation sites of cracks which grow with an increase of neutron uence by means of the connection of the pores between themselves, gradually forming the volume-connected network of cracks. Annealing at 1123 K for 5 h leads to the increase in quantity of helium at the grain boundaries due to an increase of diffusion of the gas atoms. The evolution of the already available pores to the gas bubbles occurs. This plays a dominant role in mechanisms of the radiation swelling and embrittlement of beryllium. Acknowledgements Heartily thank Dr. V. Borodin from RRC Kurchatov Institute, Russia, who has suggested the idea of the work, Dr. P. Vladimirov from KIT, Germany for fruitful discussions in the beryllium theory, and Dr. R. Melder from RIAR, Russia for the technical support to provide the irradiation for the samples. References
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