Hydrogen induced vacancy formation in tungsten

S.C. Middleburgh, R.E. Voskoboynikov, M.C. Guenette, D.P. Riley

Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, Lucas Heights, New South Wales, Australia
Abstract Atomic scale modelling methods have been used to study the change in vacancy population when H is introduced into the W bulk matrix. Schottky defects are predicted to dominate in pure W, and the vacancy concentration is expected to be very small. A mechanism whereby H solutes facilitate vacancy formation has been outlined and a single H interstitial is predicted to reduce the Schottky formation energy from 2.96 eV to 1.62 eV. Clustering of H interstitials in W facilitates vacancy formation even further: the vacancy formation energy is predicted to be 0.74 eV when two bound H interstitials are considered. H has also been shown to aect the vacancy binding characteristics in W, changing the behaviour from a repelling interaction in pure W, retarding the formation of small vacancy clusters, to an attractive interaction when vacancy-H clusters are considered. The changes in defect behaviour predicted, will have observable implications to operational properties and the application of W in fusion reactor components.

Introduction

The use of high purity tungsten for plasma facing components in thermonuclear fusion devices, such as rst-wall and divertor armour, is well established [1, 2]. Future designs of fusion reactors rely on tungstens unique physical properties of an extreme melting temperature (3410 K) and low

atomic sputtering yield to retain integrity in the fusion environment, whilst high values for thermal conductivity and heat capacity maintain thermal transfer eciencies. Although these properties are under continuing development via improved alloy chemistries [3], coordinated eorts of several major programs [1, 2] have successfully advanced the processing and fabrication of tungsten components via alternative means, aimed at reducing the impact of embrittlement and thermal shock constraints of pure tungsten [4]. Foremost amongst these advances, is the deliberate manipulation of material microstructures, facilitating the use of original manufacturing techniques at a fraction of the cost and complexity of traditional high temperature, refractory processing. Secondary eects of microstructural controls, in particular the elongated grains resulting from hot rolling, have produced tungsten materials with sucient ductility to allow for macroscopic deformation processes, e.g. deep drawing. This microstructural approach has seen immediate application in the successful manufacture of thimbles as used in multi-component divertor armour [1, 5] , but remains restricted by lower grain size limits. A potential solution to grain size renement is alloy development. Alloying is somewhat problematic due to the potential for increased transmutation eects [3]. Considering the H-eect on the mechanical properties of tungsten within fusion plasma in a wider cross-disciplinary context, it can be applied for facilitated fabrication of structural elements via the use of hydrogen during processing similar to [6]. To date, the development of tungsten alloys for use in fusion devices has considered primary damage formation [7]-[9], recovery [10]-[19], swelling [20]-[25], D-T induced transmutations [26]-[33], radiation embrittlement [10], [34]-[38] and the radiation degradation of dispersions strengthened tungsten [36], [39]-[44]. Excluding radiation damage eects, tungsten interactions with -particles and hydrogen isotopes have primarily focused on blistering [45]-[55], fuzz formation [56, 57] and deuterium/tritium retention [48]-[51], [58]-[73]. Considering this extensive research eort, material degradation on a macroscopic scale remains unexpectedly high in certain operating conditions [74] that include the high temperature, high pressure saturation of tungsten with hydrogen, resulting in an observed contraction of the unit cell lattice parameters [75]-[102]. This mechanism, was ascribed to the formation of vacancy-H clusters. The increase in vacancy concentration in the presence of

hydrogen far exceeds the expected concentration at thermodynamic equilibrium in the pure metal. The research that has been undertaken suggested that terminating surfaces act as a source of Schottky vacancies, while fusion specic investigations identied that Frenkel defects dominate after recovery from neutron induced cascades. Furthermore, additional studies outlined that residual interstitial atoms and their clusters form highly mobile dislocation loops that migrate readily away from damage regions [103, 104], while residual vacancies may trap hydrogen and form vacancy-H complexes. Related simulation via 1st principles conrmed the potential for hydrogen retention at tungsten vacancies [105, 106], suggesting a potential activation mechanism for fusion components via retention of tritium. There is some experimental evidence to suggest that H isotope induced vacancy formation can occur. Thermal desorption spectroscopy results have shown 38 eV deuterium ions can be retained with a trapping energy of 1.45 eV [48]. This energy is higher than that of previously observed low temperature traps caused by intrinsic defects, and has been designated an ion induced trap [62]. Positron annihilation spectroscopy results have demonstrated that recrystallised tungsten exposed to 38 eV deuterium ions leads to an increased vacancy concentration, despite 38 eV being well below the energy required for deuterium to displace tungsten atoms [50, 107]. While vacancy concentration remain consistent under equilibrium conditions, potential mass de-trapping of hydrogen from vacancies may result from highly non-equilibrium thermal transients. Such transient thermal excitations may occur during fusion operations, resulting in the formation of a super-saturation of vacancies within tungsten. These vacancies devoid of hydrogen may cluster, forming voids. A drastic reduction of the melting point, as observed in the Fe-H system [78], is also possible. In this work we consider an alternative mechanism by which hydrogen aects the vacancy formation energy and hence concentration of vacancies in tungsten. Using Density Functional Theory (DFT) we investigated the energetics of point defect generation in the presence of excess of hydrogen relevant to conditions prevalent in fusion applications and tungsten component fabrication. In Section 3.1 we explored the vacancy concentration in pure tungsten. We then explore the role of hydrogen in lowering the vacancy formation energy in tungsten. Additional details are provided in

Sections 3.2 and 3.3, during which we have considered the role of clustering on vacancy behaviour in tungsten under higher internal H content.

Approach and methodology

DFT calculations using the Vienna Ab-initio Simulation Package [79, 80] were carried out employing the supplied plane augmented wave (PAW) pseudopotentials with the Generalised Gradient Approximation exchange correlation as described by Perdew, Burke and Ernzerhof (GGA-PBE) supplied with the code [81]. A 444 super-cell of BCC-W was used that contained 128 atomic sites. A 333 k -point grid was used with a 500 eV cut-o energy that provided an accuracy over 102 eV per unit cell. The calculated defect energies are used in combination with each-other to evaluate the eect of H on the formation of vacancies in W (via Schottky and Frenkel processes). They were calculated using geometrically optimised structures with no symmetry constraints and under zero pressure. The vacancy formation energies were evaluated by taking the energy dierence between a perfect super-cell and a super-cell harbouring a defect, considering the atoms added or removed from an arbitrary, non-interacting position from outside of the system (N.B. this is not a defect formation energy). The calculations employed a standard approach used previously in a number of studies [82, 83]. The approach chosen was compared to two others: a method that xed the super-cell containing a defect to experimental lattice parameters and another method that xed the lattice parameters to that of perfect W that DFT predicts under zero pressure. Three alternate potential forms and three alternate super-cell sizes were also tested. The comparison of the methods is given in the Appendix. This testing highlighted the variation in results expected with each method and justied methods used throughout this study.

Atomic scale modelling results and discussion

The defect energies are reported in Table 1. The most stable H defect clusters were identied by
1 1 populating the ( 2 , 2 ,0) sites as carried out in previous work [105].

Table 1: The calculated energy of point defects and vacancy-H clusters in tungsten.
Defect Type W Vacancy W Interstitial Divacancy Description 1st nearest neighbour 2nd nearest neighbour 3rd nearest neighbour 4th nearest neighbour 5th nearest neighbour 1 1 (2 , 2 ,0) site 1st nearest neighbour 2nd nearest neighbour 3rd nearest neighbour 4th nearest neighbour 5th nearest neighbour 6th nearest neighbour lowest energy arrangement lowest energy arrangement lowest energy arrangement lowest energy arrangement Kr oger-Vink [108] VW Wi {2VW }1nn {2VW }2nn {2VW }3nn {2VW }3nn {2VW }3nn Hi {2Hi }1nn {2Hi }2nn {2Hi }3nn {2Hi }4nn {2Hi }5nn {2Hi }6nn {3Hi } HW (2H)W (3H)W (4H)W (5H)W (6H)W HW (2H)W (3H)W (4H)W Energy (eV) 11.23 3.21 22.71 22.09 22.83 22.75 22.85 -0.86 -2.52 -1.74 -2.08 -1.82/-1.31 -1.73 -1.76 -2.18 9.04 6.50 4.11 1.82 -0.11 -1.98 20.42 17.67 15.01 12.44

H interstitial Bound H interstitial pair

Bound H interstitial triplet H on W vacancy 2H on W vacancy 3H on W vacancy 4H on W vacancy 5H on W vacancy 6H on W vacancy H on 2W vacancies 2H on 2W vacancies 3H on 2W vacancies 4H on 2W vacancies

3.1

Vacancy formation in ideal BCC tungsten

The defect energies reported in Table 1 used together with the energy of a unit of W solid (-8.27 eV1 ) can be employed to investigate the equilibrium defect behaviour in the system. The Schottky defect formation energy in the absence of H can simply be calculated by considering the following equation: WW VW + W(s) (1)

1 This energy was calculated by dividing the total binding energy of the perfect W super-cell and dividing by the number of atoms (i.e. 128 in our case).

where WW is a regular W atom on its lattice site, VW is a vacant W site and W(s) is a unit of W solid [108]. Vacancy formation via reaction (1) is calculated to proceed with Ef =2.96 eV within a 444 super-cell. This compares to 3.16 eV in a 333 super-cell showing a system size dependency (see Appendix for further details). The change in unit cell volume ( V) observed due to one vacancy (0.78 % vacancy concentration) compared to the perfect W unit cell volume was -0.117 A3 , a contraction. Using the laws of mass action [109] the concentration of vacancies in pure W is 1.09108 (at 2000 K, close to
2 3

Tm [110]). When considering the potential for formation of vacancy clusters it

is essential to consider the binding of two vacancies. This was achieved by evaluating vacancies in the rst nearest neighbour to the fth nearest neighbour positions. Following the same approach, the energy of a divacancy is calculated and the corresponding equilibrium concentration varies from 2.831016 (Ef = 6.17 eV) in a 1st nearest neighbour position to 1.261016 (Ef = 6.31 eV) in a 5th nearest neighbour position. The binding energies were calculated using the following reaction: 2VW {2VW }x .n.n. (2)

The binding energies for 1st to 5th nearest neighbour vacancies were calculated to be 0.24 eV, 0.63 eV, 0.36 eV, 0.28 eV and 0.38 eV, respectively. The low concentration and positive binding energy infer that existence of divacancies in tungsten can be neglected. By comparison, the Frenkel defect formation energy for W was calculated to be 14.44 eV, considerably higher than the vacancy formation energy via Schottky mechanism and hence Frenkel pair defects will be at negligible concentration under thermodynamic equilibrium conditions. This conrms that the dominant intrinsic defect in pure W is the Schottky defect, as is normal for elemental metallic systems [111]. Given the intrinsic defect behaviour, one expects W to perform as a typical refractory metal with high ductile-to-brittle transition temperature. We now suggest a mechanism involving H that aects the vacancy population, deviating the material properties from the ideal values.

3.2

The eect of hydrogen on vacancy formation in tungsten

H solutes, in the absence of W vacancies, will take up an interstitial position. Solution of H gas into W by the following reaction was predicted to proceed with an energy of 2.53 eV (i.e. hydrogen solution is not favourable under thermodynamic equilibrium conditions): 1 H2 Hi 2 ( V = 0.113 A3 at 0.78 % concentration) (3)

Therefore, H can only be introduced into the system by non-equilibrium methods, for example, an ion implantation mechanism [112]. Within a fusion device, such phenomena occur by plasmamaterial interactions accompanied by formation of Frenkel defects. However, further vacancies can be induced in the W system if one considers the role of H interstitials: WW + Hi HW + W(s) ( V = 0.015 A3 at 0.78 % concentration) (4)

This vacancy formation was predicted to proceed with an energy of 1.62 eV which is signicantly lower than the 2.96 eV as previously calculated for single vacancy formation in the absence of H. As a result, the equilibrium concentration of vacancies in W following the introduction of H is expected to be larger. The estimated decreased Schottky formation energy will result in a more mobile W lattice, increasing diusion, potentially lowering the melting temperature, increasing crystal plasticity, and reducing thermal conductivity. Desorption of H from the W lattice will occur with temperature and will be considered elsewhere. The total strain on the lattice is also observed to be far lower when a vacancy traps H. We have already reported that vacancies have a large negative defect volume (-0.117 A3 ), while isolated H interstitial defects have a large positive defect volume (0.113 A3 ). When combined the vacancy-H cluster defect volume is -0.015 A3 , far smaller indicating that the crystal lattice is less frustrated and the defects are more stable in a bound state. The ease of vacancy formation may be increased even further if defect clustering occurs. These potential eects are dependent on the stability of the bound defects. The binding energy between two H interstitials as a function of separation is illustrated in Figure 1. A negative binding energy for nearest neighbour H-H interstitials is evident and becomes signicant at a separation distance less than 3 A. Clustering is therefore considered to be thermodynamically favourable. 7

0 .5 0 0 .2 5

B in d in g E n e r g y ( e V )

0 .0 0 -0 .2 5 -0 .5 0 -0 .7 5 -1 .0 0 1 .5 2 .0 2 .5 3 .0 3 .5 4 .0 4 .5 5 .0

H y d r o g e n - H y d r o g e n In te r s titia l D is ta n c e ( A n g s tr o m )
Figure 1: Binding energy of two hydrogen interstitial defects in tungsten as a function of their separation (the fourth nearest neighbour is considered from two symmetrically distinct sites at the same distance).

In considering the formation of multi-H clusters in W, the energy for a vacancy to be created in the presence of a double H interstitial can be calculated by: WW + {2Hi } {2H}W + W(s) ( V = 0.002 A3 at 0.78 % concentration) (5)

This reaction is predicted to proceed with an energy of 0.74 eV, which is signicant in that it is lower than both the normal Schottky formation energy in W (2.96 eV) and still lower than the vacancy formation energy in the presence of a single H interstitial (1.62 eV). Figure 2 illustrates the eect of the lower vacancy formation energy, plotting the equilibrium concentration of vacancies predicted by the laws of mass action [109]. Figure 2 was compiled assuming excess of H solutes within the W lattice and that the material had come to complete equilibrium with its environment. The change in volume associated with the defect compared to the perfect W lattice is minimised further indicating even less frustration of the lattice.
1 0 .1 0 .0 1 1 E -3 1 E -4
V a c a n c y c o n c e n tr a tio n w ith { 2 H }
W

d e fe c ts

V a c a n c y c o n c e n tr a tio n w ith H
W

d e fe c ts

V a c a n c y c o n c e n tr a tio n in id e a l tu n g s te n

V a c a n c y C o n c e n tr a tio n

1 E -5 1 E -6 1 E -7 1 E -8 1 E -9 1 E -1 0 1 E -1 1 1 E -1 2 1 E -1 3 1 E -1 4 1 E -1 5 0 2 5 0 5 0 0 7 5 0 1 0 0 0 1 2 5 0 1 5 0 0 1 7 5 0 2 0 0 0

T e m p e ra tu re (K )

Figure 2: Predicted equilibrium concentration of vacancies in tungsten metal with and without the presence of hydrogen solutes in the lattice. Two dierent types of hydrogen containing defect are considered: (1) single hydrogen defects associated with each vacancy (red line) and (2) two hydrogen defects considered with each vacancy (black dash-doted line). Thermal desorption of hydrogen from the tungsten lattice is not taken into account.

Figure 3 summarises the eect of H interstitials on the formation of W vacancies and provides the stable geometries that form as a result of vacancy formation. Notice the relaxation of the H species towards the vacant W site upon creation.

Figure 3: The formation of a vacancy via a Schottky mechanism is shown in pure tungsten (i), in tungsten in the presence of a single H (ii) and in tungsten in the presence of a two bound H interstitial defects (iii). Hydrogen species are shown as white spheres, the vacancy as a cube and tungsten species as dark blue spheres. For completeness, vacancy formation via the interaction of three H interstitial defects may be expected to proceed if the H interstitials preferentially bind by the following interaction: Hi + {2Hi } {3Hi } (6)

However, consideration of this reaction predicts it to proceed with a positive energy of 1.20 eV and hence, is unlikely. It is therefore predicted that clustering of multiple H interstitials, {xHi }, where x 3, is highly improbable.

10

Intrinsic vacancies within the W matrix or those formed by irradiation, such as plasma or neutron interaction, can be considered as potential trap sites. These vacancies attract H interstitials via the following reaction: VW + H i HW (7)

This reaction proceeds with an energy of -1.33 eV and allows for preferential accommodation of a H into a pre-existing vacancy. Further H interstitial defects will be attracted to this vacancy, as previously predicted [105] via the following reactions: HW + Hi (2H)W + (1.69 eV ), (2H)W + Hi (3H)W + (1.53 eV ), (3H)W + Hi (4H)W + (1.44 eV ), (4H)W + Hi (5H)W + (1.07 eV ), (5H)W + Hi (6H)W + (1.01 eV ), (8) (9) (10) (11) (12)

i.e. H solutes have a high driving force to trap around vacant W sites. Conversely, thermal excitations will result in the opposite reactions causing the dissociation of H from the vacancy. Although the Frenkel defect formation mechanism is far less favourable in W compared with Schottky defects, they are still of importance when the W crystal is damaged by irradiation. The H will have a small eect on the Frenkel formation energy, lowering it to 13.34 eV from an original value of 14.44 eV. Although this is not a large energy dierence, the additional damage imposed within the structure may be of signicance when considering the total life-time structural integrity of W components.

3.3

Vacancy clustering due to hydrogen

As previously shown in Section 3.1 the concentration of divacancies is negligible. This would ensure that single vacancies form a uniform distribution throughout the W crystal. In order to investigate

11

the role of H on the potential clustering of vacancies, calculations were performed by introducing 1 4 H atoms into a divacancy (populating nearest neighbour interstitial sites). The following general reaction was used to calculate the binding energy: {x H}W + {y H}W {{x H}W : {y H}W } (13)

These calculations show the binding energies between two W vacancies become negative only when associative number of H atoms 2 (as shown in Figure 4). Note then that a single associative H

does not induce binding of vacancies.

0 .2 0 .1

B in d in g E n e r g y ( e V )

0 .0 -0 .1 -0 .2 -0 .3 -0 .4 -0 .5 -0 .6 1 2 3 4

N u m b e r o f H y d ro g e n A to m s
Figure 4: Binding energy of two tungsten vacancies to a nearest neighbour position with increasing numbers of hydrogen associated with the cluster. The lowest energy cluster arrangement that was identied when four hydrogen atoms are associated with two vacancies is illustrated in Figure 5. Two hydrogen atoms coordinate in a nearest and second nearest neighbour position to each vacancy forming a highly symmetric defect cluster.

12

Figure 5: The lowest energy arrangement of four hydrogen atoms (white spheres) associated with two tungsten vacancies (cubes) in body centred cubic tungsten.

Summary

Atomic scale computer simulations have predicted a decrease in the W vacancy formation energy in the presence of H from an original 2.96 eV in the perfect material to 1.62 eV. The most apparent eect of lowering the vacancy formation energy is an increase in vacancy population. Further consideration of multiple vacancy-H interactions was shown to conclude that two H interstitial defects will attract and lower the vacancy formation energy further from 1.62 eV to 0.74 eV. Findings of this work suggest that H not only promotes vacancy formation in W but once formed the vacancy will also accommodate further H clustering. De-trapping of H from the vacancy to an interstitial position has been predicted to be energetically unfavourable (>1 eV). Of importance, this work has shown that there is potential for vacancies in W to bind to oneanother in the presence of H. This is not the case for vacancies in W in the absence of H. The coalescence of vacancies to larger vacancy clusters may be the driving force for larger void/bubble formation which could in turn lead to a signicant micro-structural evolution, not expected in pure W. Macroscopically these eects may manifest as gross variance in physical properties. 13

Thermally induced dissociation of vacancy-H clusters will result in a nite lifetime for any resultant vacancy population that exceeds the equilibrium concentration (i.e. a rise in vacancy formation energy will result in fewer vacancies in the bulk).

Appendix
We tested the eect of system size, method and pseudopotential on the Schottky vacancy formation energy, Eqn. 1, the results of which are reported in Table 2. Three dierent super-cell sizes were considered: 222, 333 and 444 containing 16, 54 and 128 lattice sites, respectively. Four dierent pseudopotentials were considered (all supplied with the VASP package [79, 80]): two that use the GGA-PBE exchange correlation with 6 and 12 electrons treated as valance, and two that use the LDA exchange correlation with 6 and 12 electrons treated as valance. Three methods were used to calculate the energies for the perfect and defective super-cells: the rst being calculations carried out at zero pressure allowing both the internal coordinates of the atoms and the volume of both perfect and defective super-cells to vary; the second being set have the lattice parameter xed to an experimental value (3.16475 A [113]) and the third having the lattice parameter of the defective cell xed to the values calculated of the perfect super-cell at zero pressure. Table 2: Schottky vacancy formation energies (eV) calculated using a range of methods (allowing lattice parameter a to relax at zero pressure or xing it to either the experimental value or perfect crystal DFT value), pseodopotentials (two dierent valance electron values for both GGA-PBE and LDA exchange correlations) and system sizes (222, 333 and 444).
super-cell 222 Method Fully Relaxed Experimental a DFT a Fully Relaxed Experimental a DFT a Fully Relaxed Experimental a DFT a GGA-PBE (12 valance electons) 3.40 3.37 3.53 3.15 3.12 3.13 2.95 3.07 2.74 GGA-PBE (6 valance electons) 3.53 3.62 3.66 3.34 3.33 3.36 3.32 3.26 3.26 LDA (12 valance electons) 3.50 3.92 3.71 3.19 3.65 3.46 3.13 3.61 3.58 LDA (6 valance electons) 3.62 4.17 3.87 3.24 3.80 3.50 3.18 3.76 3.62

333

444

14

It is clear that all variables have a distinct eect on the Schottky vacancy formation energy. Increasing the number of electrons that are considered to be bonding lowers the vacancy formation energy in using all super-cell sizes and exchange correlation avours. We have chosen to use the greater number of valance electrons as possible for our defect energy calculations as this will allow a more realistic approach to metallic bonding to be reproduced by the calculations. Table 2 reports a trend of decreasing Schottky vacancy formation energy with increase in system size. As the larger cell lowers the extent of defect-defect interactions due to the periodic boundary conditions used in this super-cell approach, the defect calculations were carried out in the 444 super-cell. The GGA-PBE calculations are consistently lower than the LDA calculations - this is to be expected as the LDA is known to over-estimate the bonding in a system (and as such overestimate the Schottky defect formation energy) whereas GGA type exchange correlations are known to slightly under-estimate bonding [114]. The three methods used are an interesting commentary on the philosophy of defect energy calculations - discussed in detail in previous articles [115, 116]. We have chosen to use the zero pressure calculations in this work to fully understand the role of extrinsic defects (here H) in W without imposing excess external pressures that may inuence the enthalpies of formation that we intend to calculate. External pressures will necessarily be imposed on the calculations when xing the lattice parameter in any way. Although all methods have their drawbacks (ours being the inuence of defect concentration of cell parameter - which can also be a useful measure - see REF) the method presented will provide useful values to guide experimental observations.

References
[1] M. Rieth, S.L. Dudarev, S.m. Gonzalez de Vincente et al., Recent progress in research on tungsten materials for nuclear fusion applications in Europe, J. Nucl. Mater. 432, 482 (2013). [2] S. Wurster, N. Balus, M. Battabyal et al. Recent progress in R& D on tungsten alloys for divertor structural plasma facing materials, J. Nucl. Mater. (2013). 15

[3] X. Wu, X.S. Kong, Y.W. You, C.S. Liu, Q.F. Fang, J.L. Chen, G.N. Luo and Z. Wang, Eects of alloying and transmutation impurities on stability and mobility of helium in tungsten under a fusion environment, Nucl. Fusion 53, 073049 (2013). [4] S.J. Zinkle, G.S. Was, Materials challenges in nuclear energy, Acta Mat. 61, 735 (2013). [5] G. Ritz, T. Hirai, P. Norajitra, J. Reiser et al. Failure study of helium-cooled tungsten divertor plasma-facing units tested at DEMO relevant steady-state hear loads, Phys. Scr. T138, 014064 (2009). [6] H. Shuhui, Z. Yingying, S. Debin, Application of thermohydrogen processing to Ti6Al4V alloy blade isothermal forging, Mat. Sci. Eng: A, 561, 17 (2013). [7] J. Fikar, R. Schaeublin, Molecular dynamics simulation of radiation damage in bcc tungsten, Nucl. Instrum. and Meth., B 255, 27 (2007). [8] J. Fikar, R. Schaeublin, Molecular dynamics simulation of radiation damage in bcc tungsten, J. Nucl. Mater., 386, 97 (2009) [9] T. Troev, N. Nankov, T. Yoshiie, Simulation of displacement cascades in tungsten irradiated by fusion neutrons, Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 269, 566 (2011). [10] I.V. Gorynin, V.A. Ignatov, V.V. Rybin et al., Eects of neutron irradiation on properties of refractory metals, J. Nucl. Mater., 191, 421 (1992). [11] M. Garnkle, W.R. Witzke, W.D. Klopp, Superplasticity in Tungsten-Rhenium Alloys, Trans. Metall. Soc. AIME 245, 303 (1969). [12] Akira Hasegawa, Takashi Tanno, Shuhei Nogami, Manabu Satou, Property change mechanism in tungsten under neutron irradiation in various reactors, J. Nucl. Mater., 417, 491 (2011). [13] L.K. Keys, J.P. Smith, J. Mote, High-Temperature Recovery of Tungsten after Neutron Irradiation, Phys. Rev. 176, 851 (1968).

16

[14] L.K.Keys, J.P.Smith, J.Mote, Stage III recovery in neutron irradiated tungsten, Scripta Metallurgica 1, 71 (1967). [15] B.L. Eyre, Transmission electron microscope studies of point defect clusters in fcc and bcc metals, J. Phys. F: Metal Phys. 3, 422 (1973). [16] Young-Won Kim, J.M. Galligan, Reply to some comments on recovery processes in thermal neutron irradiated tungsten, Scripta Metallurgica 13, 1097 (1979). [17] Young-Won Kim, J.M. Galligan,An annealing study of thermal neutron irradiated tungsten, J. Nucl. Mater. 69 680 (1978). [18] Young-Won Kim, J.M. Galligan, Radiation damage and stage iii defect annealing in thermal neutron irradiated tungsten, Acta Metallurgica 26, 379 (1978). [19] L.K. Keys, J. Mote, Neutron irradiation and defect recovery of tungsten, J. Nucl. Mater. 34, 260 (1970). [20] V.N. Chernikova, Ju.V. Lakhotkina, H. Ullmaierb, H. Trinkausb, P. Jungb, H.J. Bierfeldb, Helium-induced swelling in tungsten during postimplantation annealing, J. Nucl. Mater. 212, 375 (1994). [21] J.Matolich, H. Nahm, J. Mote, Swelling in neutron irradiated tungsten and tungsten-25 percent rhenium, Scripta Metallurgica, 8, 837 (1974). [22] F.W.Wien, In Refractory Alloy Technology for Space Nuclear Power Applications, CONF8308130; Cooper, R.H., Jr, Homan, E. E., Eds.; Oak Ridge National Laboratory: Oak Ridge, TN, 252277 (1984). [23] V.K.Sikka, J.Mote, Rafting in neutron irradiated tungsten, J. Appl. Phys. 43, 4942 (1972). [24] J.C. He, A.Hasegawa, K.Abe, Eects of transmutation elements on the defect structure development of W irradiated by protons and neutrons, J. Nucl. Mater. 377, 348 (2008).

17

[25] R.C.Rau, R.L.Ladd, J.Mote, Voids in irradiated tungsten and molybdenum, J. Nucl. Mater. 33, 324 (1969). [26] J.D.Heckelman, R.P.Kozar, Measured drift of irradiated and unirradiated W-3%Re/W-25%Re thermocouples at a nominal 2000 K, NASA Technical Report, NASA TM X-67818; Lewis Research Center: Cleveland, OH, (1971). [27] C. Vitanza, T.E. Stein, Assessment of fuel thermocouple decalibration during in-pile service , J. Nucl. Mater. 139, 11 (1986). [28] R.K. Williams, F.W. Wien, J. Bentley, J.O. Stiegler, Irradiation induced precipitation in tungsten based, W-Re alloys , Met. Trans. A 14, 655 (1983). [29] T. Tanno, A. Hasegawa, J.C. He, M. Fujiwara, M. Satou, S. Nogami, K. Abe, T. Shishido, Eects of transmutation elements on the microstructural evolution and electrical resistivity of neutron-irradiated tungsten, J. Nucl. Mater., 386, 218 (2009). [30] T. Noda, M. Fujita, M. Okada, Transmutation and induced radioactivity of W in the armor and rst wall of fusion reactors, J. Nucl. Mater. 258, 934 (1998). [31] Y. Nemoto, A. Hasegawa, M. Satou, K. Abe, Microstructural development of neutron irradiated WRe alloys, J. Nucl. Mater. 283, 1144 (2000). [32] R. Behrisch, V. Khripunov, R.T. Santoro, J.M. Yesil, Transmutation of plasma facing materials by the neutron ux in a DT fusion reactor, J. Nucl. Mater. 258, 686 (1998) [33] R. Van Nieuwenhove, L. Vermeeren, Irradiation eects on temperature sensors for ITER application, Rev. Sci. Instrum. 75, 75 (2004). [34] J.M. Steichen, Tensile properties of neutron irradiated TZM and tungsten , J. Nucl. Mater. 60, 13 (1976). [35] K. Ueda, M.Satou, A.Hasegawa, K. Abe, Deformation analysis of small size bend specimens by FEM calculation to estimate irradiation induced embrittlement of Mo and W, J. Nucl. Mater. 258, 466 (1998) 18

[36] Y. Kitsunai, H. Kurishita, H. Kayano, Y. Hiraoka, T. Igarashi, T. Takida, Microstructure and impact properties of ultra-ne grained tungsten alloys dispersed with TiC, J. Nucl. Mater. 271, 423 (1999). [37] M. Fukuda, A. Hasegawa, T. Tanno, S. Nogami, H. Kurishita, Property change of advanced tungsten alloys due to neutron irradiation, J. Nucl. Mater. in press (2013). [38] R.C. Rau, J. Mote, R.L. Ladd, Comparison of microstructure with mechanical properties of irradiated tungsten, J. Nucl. Mater. 24, 164 (1967). [39] Gui-Ming Song, Yu-Jin Wang, Yu Zhou, Thermomechanical properties of TiC particlereinforced tungsten composites for high temperature applications, International Journal of Refractory Metals and Hard Materials 21, 1 (2003). [40] Y. Chena, Y.C. Wu, F.W. Yu, J.L. Chen, Eect of rare earth La2 O3 on the microstructure and mechanical properties of T iC/W composites, Rare Metals 27, 632 (2008). [41] Y. Chena, Y.C. Wu, F.W. Yu, J.L. Chen, Microstructure and mechanical properties of tungsten composites co-strengthened by dispersed T iC and La2 O3 particles, International Journal of Refractory Metals and Hard Materials 26, 525 (2008). [42] M. Battabyal, R. Sch aublin, P. Sp atig, N. Baluc, W 2wt.%Y2 O3 composite: Microstructure and mechanical properties, Materials Science and Engineering: A 538, 53 (2012). [43] M. Battabyal, R. Sch aublin, P. Sp atig, M. Walter, M. Rieth, N. Baluc, Microstructure and mechanical properties of a W 2wt.%Y2 O3 composite produced by sintering and hot forging, J. Nucl. Mater. http://dx.doi.org/10.1016/j.jnucmat.2013.01.301 (2013). [44] M. Battabyal, P. Sp atig, N. Baluc, Eect of ion-irradiation on the microstructure and microhardness of the W 2Y2 O3 composite materials fabricated by sintering and hot forging, Fusion Engineering and Design, http://dx.doi.org/10.1016/j.fusengdes.2013.03.060 (2013).

19

[45] Y. Ueda, T. Funabiki, T. Shimada, K. Fukumoto, H. Kurishita, M. Nishikawa, Hydrogen blister formation and cracking behavior for various tungsten materials, J. Nucl. Mater. 337, 1010 (2005). [46] M.Y. Ye, H. Kanehara, S. Fukuta, N. Ohno, S. Takamura, Blister formation on tungsten surface under low energy and high ux hydrogen plasma irradiation in NAGDIS-I, J. Nucl. Mater. 313, 72 (2003). [47] Dai Nishijima, M.Y Ye, N Ohno, S Takamura, Formation mechanism of bubbles and holes on tungsten surface with low-energy and high-ux helium plasma irradiation in NAGDIS-II, J. Nucl. Mater. 329, 1029 (2004). [48] W.M. Shu, G.-N. Luo, T. Yamanishi, Mechanisms of retention and blistering in near-surface region of tungsten exposed to high ux deuterium plasmas of tens of eV, J. Nucl. Mater. 367, 1463 (2007). [49] W.M. Shu, K. Isobe, T. Yamanishi, Temperature dependence of blistering and deuterium retention in tungsten exposed to high-ux and low-energy deuterium plasma, Fusion Engineering and Design 83, 1044 (2008). [50] W.M. Shu, A. Kawasuso, T. Yamanishi, Recent ndings on blistering and deuterium retention in tungsten exposed to high-uence deuterium plasma, J. Nucl. Mater. 386, 356 (2009). [51] W.M. Shu, M. Nakamichi, V.Kh. Alimov, G.-N. Luo, K. Isobe, T. Yamanishi, Deuterium retention, blistering and local melting at tungsten exposed to high-uence deuterium plasma, J. Nucl. Mater. 390, 1017 (2009). [52] Wenmin Wang, J Roth, S Lindig, C.H Wu, Blister formation of tungsten due to ion bombardment, J. Nucl. Mater. 299, 124 (2001). [53] T. Funabiki, T. Shimada, Y. Ueda, M. Nishikawa, Eect of tungsten microstructure on blister formation by hydrogen and carbon mixed ion beam irradiation, J. Nucl. Mater. 329, 780 (2004).

20

[54] T. Shimada, Y. Ueda, M. Nishikawa, Mechanism of blister formation on tungsten surface, Fusion Engineering and Design 66, 247 (2003). [55] K. Tokunaga, M.J. Baldwin, R.P. Doerner, N. Noda, Y. Kubota, N. Yoshida, T. Sogabe, T. Kato, B. Schedler, Blister formation and deuterium retention on tungsten exposed to low energy and high ux deuterium plasma, J. Nucl. Mater. 337, 887 (2005). [56] M.J. Baldwin and R.P. Doerner, Helium induced nanoscopic morphology on tungsten under fusion relevant plasma conditions, Nucl. Fusion 48, 035001 (2008). [57] M.J. Baldwin and R.P. Doerner, Formation of helium induced nanostructure fuzz on various tungsten grades, J. Nucl. Mater. 404, 165 (2010). [58] T. Hino, Y. Yamauchi, Y. Kimura, K. Nishimura, Y. Ueda, Fuel hydrogen retention of tungsten and the reduction by inert gas glow discharges, Fusion Engineering and Design 87, 876 (2012). [59] M. Shimada, Y. Hatano, Y. Oya, T. Oda, M. Hara, G. Cao, M. Kobayashi, M. Sokolov, H. Watanabe, B. Tyburska-P uschel, Y. Ueda, P. Calderoni, K. Okuno, Overview of the USJapan collaborative investigation on hydrogen isotope retention in neutron-irradiated and ion-damaged tungsten, Fusion Engineering and Design 87, 1166 (2012). [60] Y. Oya, M. Kobayashi, R. Kurata, N. Yoshida, N. Ashikawa, A. Sagara, M. Hara, Y. Hatano, K. Okuno, Comparison of hydrogen isotope retention and irradiation damage behaviors in
+ tungsten and SS-316 with simultaneous C + D2 implantation, Fusion Engineering and Design

86, 1776 (2011). [61] G.-N. Luo, , W.M. Shu, M. Nishi, Inuence of blistering on deuterium retention in tungsten irradiated by high ux deuterium 10100 eV plasmas, Fusion Engineering and Design 81, 957 (2006). [62] O.V. Ogorodnikova, J. Roth, M. Mayer, Deuterium retention in tungsten in dependence of the surface conditions, J. Nucl. Mater. 313, 469 (2003).

21

[63] Y. Oya, S. Masuzaki, M. Tokitani, N. Yoshida, H. Watanabe, Y. Yamauchi, T. Hino, M. Miyamoto, Y. Hatano, K. Okuno, Enhancement of hydrogen isotope retention capacity for the impurity deposited tungsten by long-term plasma exposure in LHD, Fusion Engineering and Design, http://dx.doi.org/10.1016/j.fusengdes.2013.03.002 (2013). [64] A.V. Golubeva, M. Mayer, J. Roth, V.A. Kurnaev, O.V. Ogorodnikova,Deuterium retention in rhenium-doped tungsten, J. Nucl. Mater. 363 893 (2007). [65] P . Wang, W. Jacob, L. Gao, T. D urbeck, T. Schwarz-Selinger, Comparing deuterium retention in tungsten lms measured by temperature programmed desorption and nuclear reaction analysis, Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 300, 54 (2013). [66] R Causey, K Wilson, T Venhaus, W R. Wampler,Tritium retention in tungsten exposed to intense uxes of 100 eV tritons, J. Nucl. Mater. 266, 467 (1999). [67] M. Poon, A.A. Haasz, J.W. Davis, R.G. Macaulay-Newcombe, Impurity eects and temperature dependence of D retention in single crystal tungsten, J. Nucl. Mater. 313, 199 (2003). [68] D. Nishijima, T. Sugimoto, H. Iwakiri, M.Y. Ye, N. Ohno, N. Yoshida, S. Takamura, Characteristic changes of deuterium retention on tungsten surfaces due to low-energy helium plasma pre-exposure, J. Nucl. Mater. 337, 927 (2005). [69] A.A. Haasz, M. Poon, R.G. Macaulay-Newcombe, J.W. Davis,Deuterium retention in single crystal tungsten, J. Nucl. Mater. 290, 85 (2001). [70] M. Tokitani, M. Miyamoto, K. Tokunaga, T. Fujiwara, N. Yoshida, S. Masuzaki, N. Ashikawa, T. Morisaki, M. Shoji, A. Komori, LHD Experimental Group dS. Nagata, B. Tsuchiya, Retention properties of plasma particles in tungsten exposed to LHD divertor plasmas, J. Nucl. Mater. 363, 443 (2007). [71] V.Kh. Alimov, K. Ertl, J. Roth, Deuterium retention and lattice damage in tungsten irradiated with D ions, J. Nucl. Mater. 290, 389 (2001). 22

[72] Z. Tian, J.W. Davis, A.A. Haasz, Deuterium retention in tungsten at uences of up to 1026 D+ /m2 using D+ ion beams, J. Nucl. Mater. 399, 101 (2010). [73] G. Maddaluno, G. Giacomi, A. Rufoloni, L. Verdini, Deuterium retention and surface modication of tungsten macrobrush samples exposed in FTU Tokamak, Volumes 363 1236 (2007). [74] F. Sefta, K.D. Hammond, N. Juslin, B.D. Wirth, Tungsten surface elcolution by helium bubble nucleation, growth and rupture, Nucl. Fusion 53, 073015 (2013). [75] S. Harada, S. Yokota, Y. Ishii, Y. Shizuku, M. Kanazawa, Y. Fukai, A relation between the vacancy concentration and hydrogen concentration in the Ni-H, Co-H and Pd-H systems, Journal of Alloys and Compounds, 404, 247-251 (2005). [76] N. Fukumuro, M. Yokota, S. Yae, H. Matsuda, Y. Fukai, Hydrogen-induced enhancement of atomic diusion in electrodeposited Pd lms, Journal of Alloys and Compounds, http://dx.doi.org/10.1016/j.jallcom.2013.02.111 (2013). [77] Y. Shizuku, S. Yamamoto, Y. Fukai, Phase diagram of the NiH system at high hydrogen pressures, Journal of Alloys and Compounds, 336, 159 (2002). [78] H. Osono, T. Kino, Y. Kurokawa, Y. Fukai, Agglomeration of hydrogen-induced vacancies in nickel, Journal of Alloys and Compounds, 348, 105 (2003). [79] G. Kresse, J. Hafner, Ab initio molecular dynamics for liquid metals , Phys. Rev. B 47, 558 (1993). [80] G. Kresse, D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B 59, 1758 (1999). [81] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77, 3865 (1996). [82] S.C. Middleburgh, D.C. Partt, P.R. Blair, R.W. Grimes, Atomic scale modeling of point defects in zirconium diboride, J. Am. Ceram. Soc. 94, 2225 (2011).

23

[83] S.C. Middleburgh, K.P.D. Lagerlof, R.W. Grimes, Accommodation of Excess Oxygen in Group II Monoxides , J. Am. Ceram. Soc. 96, 308 (2013). [84] Y. Fukai, M. Mizutani, S. Yokota, M. Kanazawa, Y. Miura, T. Watanabe, Superabundant vacancyhydrogen clusters in electrodeposited Ni and Cu, Journal of Alloys and Compounds, 356, 270 (2003). [85] Y. Fukai, From metal hydrides to the metal-hydrogen system, Journal of the Less Common Metals 172, 8 (1991). [86] T. Iida, Y. Yamazaki, T. Kobayashi, Y. Iijima, Y. Fukai,Enhanced diusion of Nb in Nb-H alloys by hydrogen-induced vacancies, Acta Materialia, 53 Issue 10, 3083 (2005). [87] Y. Fukai, T. Haraguchi, H. Shinomiya, K. Mori, Constitution of the Mn-H system at high hydrogen pressures, Scripta Materialia, 46, 679 (2002). [88] Y. Fukai,Site preference of interstitial hydrogen in metals, Journal of the Less Common Metals 101, 1 (1984). [89] Y. Fukai, Formation of superabundant vacancies in M-H alloys and some of its consequences: a review, Journal of Alloys and Compounds, 356, 263 (2003). [90] Y. Fukai, Y. Ishii, Y. Goto, K. Watanabe, Formation of superabundant vacancies in PdH alloys, Journal of Alloys and Compounds, 313, 121 (2000). [91] Y. Fukai, S. Yokota, J. Yanagawa, The phase diagram and superabundant vacancy formation in CoH alloys, Journal of Alloys and Compounds, 407, 16 (2006). [92] Y. Fukai, Y. Shizuku, Y. Kurokawa, Superabundant vacancy formation in Ni-H alloys, Journal of Alloys and Compounds, 329, 195 (2001). [93] Y Fukai, S Yamatomo, S Harada, M Kanazawa, The phase diagram of the Ni-H system revisited, Journal of Alloys and Compounds, 372, L4-L5 (2004).

24

[94] H Sugimoto, Y Fukai, Quantum mechanical state of interstitial hydrogen in metals: Energy and wavefunctions, Journal of the Less Common Metals, 89, 307 (1983). [95] K. Sakamaki, E. Takahashi, Y. Nakajima, Y. Nishihara, K. Funakoshi, T. Suzuki, Y. Fukai, Melting phase relation of FeHx up to 20 GPa: Implication for the temperature of the Earths core, Physics of the Earth and Planetary Interiors, 174, 192 (2009). [96] K. Watanabe, N. Okuma, Y. Fukai, Y. Sakamoto, Y. Hayashi, Superabundant vacancies and enhanced diusion in Pd-Rh alloys under high hydrogen pressures, Scripta Materialia, 34, 551 (1996). [97] T. Hiroi, Y. Fukai, K. Mori, The phase diagram and superabundant vacancy formation in Fe-H alloys revisited, Journal of Alloys and Compounds, 404 252 (2005). [98] Y. Fukai, K. Mori, H.Shimoniya, The phase diagram and superabundant vacancy formation in Fe-H alloys under high pressure, Journal of Alloys and Compounds, 348, 105 (2003). [99] S. Harada, D. Ono, H. Sugimoto, Y. Fukai, The defect structure with superabundant vacancies to be formed from fcc binary metal hydrides: Experiments and simulations, Journal of Alloys and Compounds, 446, 474 (2007). [100] Y. Fukai, Formation of superabundant vacancies in metal hydrides at high temperatures, Journal of Alloys and Compounds, 231, 35 (1995). [101] Y. Fukai, K. Watanabe, A. Fukizawa, Eect of pressure on the phase transition in V2 H and V2 D, Physics Letters A, 90, 429 (1982). [102] K. Nakamura, Y. Fukai, High-pressure studies of high-concentration phases of the Ti-H system, Journal of Alloys and Compounds, 231, (1995) 46 (1982). [103] R.E. Stoller, G. R. Odette, B. D. Wirth, Primary damage formation in bcc iron, J. Nucl. Mater. 251, 49 (1997). [104] R.E. Stoller, The role of cascade energy and temperature in primary defect formation in iron, J. Nucl. Mater. 276, 22 (2000). 25

[105] K. Heinola, T. Ahlgren, K. Nordlund, and J. Keinonen, Hydrogen interaction with point defects in tungsten, Phys Rev B 82, 094102 (2010). [106] Y.L. Liu, H.-B. Zhou, Y.Zhang, Investigating behaviours of H in a W single crystal by rstprinciples: from solubility to interaction with vacancy, Journal of Alloys and Compounds, 509, 8277 (2011). [107] W.M. Shu , A. Kawasuso, Y. Miwa et al. Microstructure dependence of deuterium retention and blistering in the near-surface region of tungsten exposed to high ux deuterium plasmas of 38 eV at 315 K, Phys. Scr. 96, 2007 (2007). [108] F.A. Kroger, H.J. Vink, Relations between the concentrations of imperfections in crystalline solids, Solid State Physics 3, 307 (1956). [109] M.R. Levy, K.J.W. Atkinson, O.H. Odili, R.W. Grimes, Dielectric relaxation of lithium-doped zinc uoride, Physica B, 365, 147 (2005). [110] I. Langmuir, The melting-point of tungsten, Journal of the Franklin Institute 180, 490 (1915). [111] S.C. Middleburgh, R.W. Grimes, Defects and transport processes in beryllium, Acta Materialia 59, 7095 (2011). [112] M.R. Gilbert, S.L. Dudarev, S. Zheng et al. An integrated model for materials in a fusion power plant: transmutation, gas production, and helium embrittlement under neutron irradiation, Nucl. Fusion 52, 083019 (2012). [113] V.T. Deshpande, R. Pawar, X-ray determination of the thermal expansion of tungsten, Current Science 31, 497 (1962). [114] H. Shi, P. Zhang, S.S. Li, B. Sun, B. Wang,Electronic structures and mechanical properties of uranium monocarbide from rst-principles LDA+U and GGA+U calculations, Phys. Let. A 373, 3577 (2009). [115] M. Pukari, O. Runevall, N. Sandberg, J. Wallenius, Vacancy formation and solid solubility in the U-Zr-N system, Journal of Nuclear Materials, 406, 351 (2010). 26

[116] P. Olsson, C. Domain, J. Wallenius, Ab initio study of Cr interactions with point defects in bcc Fe, Phys. Rev. B 75, 014110 (2007).

27