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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.


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


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.


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 }

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

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.


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.


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


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.


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


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).

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




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.

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