Helium diffusion coefficient measurements in R7T7 nuclear glass by He(d,α)H nuclear reaction analysis

The immobilization of fission products and minor actinides by vitrification is the reference process for industrial management of high-level radioactive wastes generated by spent fuel reprocessing. Radiation damage and radiogenic helium accumulation must be specifically studied to evaluate the effects of minor actinide alpha decay on the glass long-term behavior under repository conditions.A specific experimental study was conducted for a comprehensive evaluation of the behavior of helium and its diffusion mechanisms in borosilicate nuclear waste glass. Helium production was simulated by external implantation with ³He ions at a concentration (≈1 at.%) 30 times higher than obtained after 10,000 years of storage. Helium diffusion coefficients as a function of temperature were extracted from the depth profiles after annealing. The ³He(d,α)¹H nuclear reaction analysis (NRA) technique was successfully adopted for low-temperature in situ measurements of depth profiles. Its high depth resolution revealed helium mobility at temperatures as low as 253 K and the presence of a trapped helium fraction. The diffusion coefficients of un-trapped helium atoms follow an Arrhenius law between 253 K and 323 K. An activation energy of 0.55 ± 0.03 eV was determined, which is consistent with a process controlled by diffusion in the glass free volume.     

Helium desorption in He implanted tungsten at low fluence and low energy

The behaviour of helium in polycrystalline ³He implanted tungsten at low energy (60 keV) and low fluence (2 × 10¹³ cm⁻²) has been studied as a function of post-implantation annealing temperature until 1873 K by means of Nuclear Reaction Analysis. Helium desorption has been observed only from ∼1500 K, suggesting a helium trapping at mono-vacancies. Only ∼75% of the implanted helium has been released after the annealing during 1 h at high temperature (1873 K); besides, the desorption rate decreased from 1673 K. The presence of a second type of helium trapping site is likely to explain this strong helium retention.     

Thermal desorption of helium from defects in nickel

Helium atoms, introduced into materials by helium plasma or generated by the (n, α) nuclear reaction, have a strong tendency to accumulate at trapping sites such as vacancy clusters and dislocations. In this paper, the effects of dislocations, single vacancies and vacancy clusters on the retention and desorption of helium atoms in nickel were studied. Low energy (0.1-0.15 keV) helium atoms were implanted in nickel with vacancies or dislocations without causing any displacement damage. He atoms, interstitial-type dislocation loops, and vacancy clusters were also introduced with irradiation damage by 5.0 keV helium ions. Helium thermal desorption peaks from dislocations, helium-vacancy clusters and helium bubbles were obtained by thermal desorption spectroscopy at 940 K, in the range from 900 to 1370 K, and at 1500 K, respectively. In addition, a thermally quasi-stable state was found for helium-vacancy clusters.     

Microstructural analysis on helium retention of ion-irradiated and annealed tungsten foils

The helium retention characteristics and helium bubble distribution in tungsten were studied using ³He(d,p)⁴He nuclear reaction analysis (NRA) and transmission electron microscopy (TEM) on two forms of tungsten: single crystal and polycrystalline, implanted to 1 × 10^19 3He/m² at 850 °C and annealed at 2000 °C. The NRA results revealed that as-implanted single crystal and polycrystalline tungsten exhibited similar helium retention characteristics. Stepwise annealing reduced the helium retention in both single crystal and polycrystalline tungsten when the number of implantation steps and annealing time were increased. The TEM results indicated that microstructure played a large role in helium trapping; the existence of grain boundaries led to significant cavity formation and greater cavity growth. Single crystal tungsten had less trapping sites for helium, allowing long range He diffusion during annealing. The decrease of He retention in polycrystalline tungsten during stepwise annealing was probably due to significant recrystallization, resulting in decrease of grain boundary density.     

Ion-irradiation-induced athermal annealing of helium bubbles in SiC

We have compared the microstructural evolution of helium bubbles under ion irradiation and high temperature annealing. 4H-SiC was irradiated first by 140 keV He ions to a fluence of 1.0 × 10¹⁷ cm⁻² and then annealed at 1200 K for 30 min. Then, the samples were either irradiated by 2 MeV He ions to a fluence of 3.0 × 10¹⁶ cm⁻² at room temperature or annealed additionally at 1200 K for 30 min. Before and after 2 MeV He ion irradiation, significant microstructural changes were observed, similar to effects of high temperature annealing. Thus, the study provides evidence of ion-irradiation-induced athermal annealing on defect Ostwald ripening process and bubble evolution. Possible mechanisms are discussed.     

Large-scale molecular dynamics simulation of sputtering process with glancing-angle Ar cluster impact on 4H-SiC

Large-scale molecular dynamics simulations with two Ar₆₈₈ cluster impacts on a 4H-SiC surface are performed to investigate the mechanism of lateral sputtering caused by two clusters collisions. The two Ar clusters are composed of 688 atoms each (referred as Ar₆₈₈) which are described by a simple Lennard-Jones potential. The initial velocities of both clusters are 2.55 × 10⁴ m/s when the acceleration voltage is 100 keV. The computational volume is 30 nm × 30 nm × 16 nm, which is constructed by 1444608 4H-SiC atoms. At 0.8 ps after the impact from the first Ar cluster on the 4H-SiC surface, a second argon cluster with predetermined incident-angle collides with 4H-SiC surface at a distance of one “diameter” away from the center of the first impact where the term “diameter” refers to the diameter of the footprint of the first impact on 4H-SiC. The incident-angle of the second argon cluster was set at 0°, 60°, or 80° for three different trials. Consequently, in each case the crater formed by the first cluster showed signs of being smeared out by the impact of the second cluster. Especially at the incident-angle of 80° the effects of surface modification were clearly noticeable.     

Helium and deuterium implantation in tungsten at elevated temperatures

High temperature helium and deuterium implantation on tungsten has been studied using the University of Wisconsin inertial electrostatic confinement device. Helium or deuterium ions from a plasma source were driven into polished tungsten powder metallurgy samples. Deuterium implantation did not damage the surface of the specimens at elevated temperatures (∼1200 °C). Helium implantation resulted in a porous surface structure above 700 °C. A helium fluence scan, ion energy scan, and temperature scan were all completed. With 30 keV ions, the pore formation started just below 4 × 10¹⁶ He⁺/cm². The pore size increased and the pore density decreased with increasing fluence and temperature. The energy scan from 20 to 80 keV showed no consistent trend.     

DIADDHEM set-up: New IBA facility for studying the helium behavior in nuclear glasses

The immobilization of fission products and minor actinides by vitrification is the reference process for industrial management of high-level radioactive wastes generated from spent fuel reprocessing. The glassy matrix is subjected to radiation damage and radiogenic helium generation due to the alpha decays of minor actinides.A specific experimental study has been conducted to better understand the behavior of helium and its diffusion mechanisms in the borosilicate glass. Helium production is simulated by external irradiation with ³He⁺ ions at a concentration (2 × 10¹⁵ He cm^?2) equivalent to the one obtained after 1000 years of glass storage. He diffusion coefficients as function of temperature are extracted from the evolution of the depth profiles after annealing. The ³He(d, α) ¹H Nuclear Reaction Analysis (NRA) technique is successfully used for in situ low-temperature measurements of depth profiles. Its high depth resolution allows detecting helium mobility at a temperature as low as 250 K and the presence of a trapped helium fraction. The good agreement of our first values of diffusion coefficients with the literature data highlights the relevance of the implantation technique in the study of helium diffusion mechanisms in borosilicate glasses.     

Temperature dependence of lattice disorder in Ar-irradiated (1 0 0), (1 1 0) and (1 1 1) MgO single crystals

To better appreciate dynamic annealing processes in ion irradiated MgO single crystals of three low-index crystallographic orientations, lattice damage variation with irradiation temperature was investigated. Irradiations were performed with 100 keV Ar ions to a fluence of 1 × 10¹⁵ Ar/cm² in a temperature interval from −150 to 1100 °C. Rutherford backscattering spectroscopy combined with ion channeling was used to analyze lattice damage. Damage recovery with increasing irradiation temperature proceeded via two characteristic stages separated by 200 °C. Strong radiation damage anisotropy was observed at temperatures below 200 °C, with (1 1 0) MgO being the most radiation damage tolerant. Above 200 °C damage recovery was isotropic and almost complete recovery was reached at 1100 °C. We attributed this orientation dependence to a variation of dynamic annealing mechanisms with irradiation temperature.     

Dynamic annealing study of SiC epilayers implanted with Ni ions at different temperatures

SiC epilayers grown on 4H-SiC single crystals were implanted with 850 keV Ni⁺ ions with fluences in the 0.5-9 × 10¹⁶ Ni⁺/cm² range. Most of the samples were implanted at 450 °C, but for comparison some implantations were performed at room temperature (RT). In addition, a post-implantation annealing was performed in N₂ at 1100 °C in order to recover the implantation-induced structural damage. The disorder produced by the implantation at 450 °C and the effect of the post-implantation annealing on the recrystallization of the substrates have been studied as a function of the fluence by Backscattering Spectrometry in channeling geometry (BS/C) with a 3.45 MeV He²⁺ beam. RT as-implanted samples showed a completely amorphous region which extends until the surface when irradiated with the highest dose, whereas in the case of 450 °C implantation amorphization does not occur. In general, partial recovery of the crystal lattice quality was found for the less damaged samples, and the dynamic recovery of the crystalline structure increases with the irradiation temperature.     

Structural and optical properties of 6H-SiC helium-implanted at 600 K

Single crystals of 6H-SiC were implanted at 600 K with 100 keV He ions to three successively fluences and subsequently annealed at different temperatures ranging from 873 to 1473 K in vacuum. The recovery of lattice damage was investigated by different techniques including Rutherford backscattering spectrometry in channeling geometry, Raman spectroscopy and Fourier transform infrared spectroscopy. All three techniques showed that the damage induced by helium ion implantation in the lattice is closely related to the fluence. Rutherford backscattering spectrometry/channeling data on high temperature implantations suggest that for a fluence of 3 × 10¹⁶ He⁺/cm², extended defects are created by thermal annealing to 1473 K. Apart from a well-known intensity decrease of scattering peaks in Raman spectroscopy it was found that the absorbance peak in Fourier transform infrared spectroscopy due to the stretching vibration of Si-C bond shifted to smaller wave numbers with increasing fluence, shifting back to larger wave numbers with increasing annealing temperature. These phenomena are attributed to different lattice damage behavior induced by the hot implantation process, in which simultaneous recovery was prevailing.     

Study of silver diffusion in silicon carbide

Diffusion of silver in 6H-SiC and polycrystalline CVD-SiC was investigated using α-particle channeling spectroscopy and electron microscopy. Fluences of 2 × 10¹⁶ cm⁻² of ¹⁰⁹Ag⁺ were implanted with an energy of 360 keV at room temperature, at 350 °C and 600 °C, producing an atomic density of approximately 2% at the projected range of about 110 nm. The broadening of the implantation profile and the loss of silver through the front surface during vacuum annealing at temperatures up to 1600 °C was determined. Fairly strong silver diffusion was observed after an initial 10 h annealing period at 1300 °C in both polycrystalline and single crystalline SiC, which is mainly due to implant induced radiation damage. After further annealing at this temperature no additional diffusion took place in the 6H-SiC samples, while it was considerably reduced in the CVD-SiC. The latter was obviously due to grain boundary diffusion and could be described by the Fick diffusion equation. Isochronal annealing of CVD-SiC up to 1400 °C exhibited an Arrhenius type temperature dependence, from which a frequency factor D_o ∼ 4 × 10⁻¹² m² s⁻¹ and an activation energy E_a ∼ 4 × 10⁻¹⁹ J could be extracted. Annealing of 6H-SiC above 1400 °C shifted the silver profile without any broadening towards the surface, where most of the silver was released at 1600 °C. Electron microscopy revealed that this process was accompanied by significant re-structuring of the surface region. An upper limit of D < 10⁻²¹ m² s⁻¹ was estimated for 6H-SiC at 1300 °C.     

Study of iodine diffusion in silicon carbide

Diffusion of iodine in 6H-SiC and polycrystalline CVD-SiC was investigated using Rutherford backscattering spectroscopy and electron microscopy. A fluence of 1 × 10¹⁶ cm⁻² of ¹²⁷I⁺ was implanted with an energy of 360 keV at room temperature, producing an amorphous surface layer of approximately 220 nm thickness. The implantation profile reached an atomic density of approximately 1.3% at the projected range of about 95 nm. Broadening of the implantation profile and iodine loss through the front surface during isochronal and isothermal vacuum annealing was determined. At a temperature of 1100 °C no iodine loss was observed after 120 h and a diffusion coefficient of less than 10⁻²¹ m² s⁻¹ was extracted from the analysis of profile widths. Relatively strong broadening occurred after 60 h annealing at 1200 °C with the iodine profile extending beyond 300 nm into the bulk, accompanied by a surprisingly modest iodine loss through the surface. Electron microscopic studies reveal a drastic restructuring of the surface region at this temperature, indicating possible chemical reactions between iodine and silicon carbide.     

The interdiffusion and solid-state reaction of low-energy copper ions implanted in silicon

At room temperature, single-crystal silicon was implanted with Cu⁺ ions at an energy of 80 keV using two doses of 5 × 10¹⁵ and 1 × 10¹⁷ Cu⁺ cm⁻². The samples were heat treated by conventional thermal annealing at different temperatures: 200 °C, 230 °C, 350 °C, 450 °C and 500 °C. The interdiffusion and solid-state reactions between the as-implanted samples and the as-annealed samples were investigated by means of Rutherford backscattering spectrometry (RBS) and X-ray diffraction (XRD). After annealing at 230 °C, the XRD results of the samples (subject to two different doses) showed formation of Cu₃Si. According to RBS, the interdiffusion between Cu and Si atoms after annealing was very insignificant. The reason may be that the formation of Cu₃Si after annealing at 230 °C suppressed further interdiffusion between Si and Cu atoms.     

Preparation of Al thin films charged with helium by DC magnetron sputtering

Helium atoms, up to 6.9 at.%, were introduced into Al films by DC magnetron sputtering in a He/Ar mixed atmosphere and distributed evenly in it. The relation between the He/Ar flux ratio, bias voltage, substrate temperature and helium concentration is studied. The helium concentration can be easily controlled by change of the process parameters and it greatly affects the morphology of film. TEM analysis suggests that small helium bubbles with a diameter of 1 nm are formed in the grain.     

Effect of thermo-mechanical processing on microstructure and creep properties of the foils of alloy 617

The effect of rolling and annealing on the microstructure and high temperature creep properties of alloy 617 were investigated. Two types of foil specimens with different thickness reductions were prepared by thermo-mechanical processing. Recrystallization and grain growth were readily observed at specimens annealed at 950 and 1100 °C. The uniform coarse grains increase resistance against creep deformation. The grain size effect in creep deformation was dominant up to 900 °C, while dynamic recrystallization effect became dominant at 1000 °C. Dynamic recrystallization was observed in all the creep deformed foils, even though some specimens had already been (statically) recrystallized during annealing. Steady state creep rates decreased with increasing annealing temperature in the less rolled foils. The apparent activation energy Q_app for the creep deformation increased from 271 to 361 kJ/mol as the annealing temperature increased from 950 to 1100 °C.     

The influence of the microstructure evolution on the surface morphology in the annealing process of helium-implanted spinel

Single-crystalline spinel (MgAl₂O₄) specimens were implanted with helium ions of 100 keV at three successively increasing fluences of (0.5, 2.0 and 8.0) × 10¹⁶ ions/cm² at room temperature. The specimens were subsequently annealed in vacuum at different temperatures ranging from 500 to 1100 °C. Different techniques, including Fourier transformed infrared spectroscopy (FTIR), thermal desorption spectrometry (TDS), atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to investigate the specimens. It was found that the absorbance peak in the FTIR due to the stretching vibration of the Al-O bond shifts to smaller wave numbers with increasing fluence, shifting back to larger wave numbers with an increase of annealing temperature. The absorbance peak shift has a linear relationship with the fluence increase in the as-implanted state, while it does not have a linear relationship with the fluence increase after the annealing process. Surface deformation occurred in the specimens implanted with fluences of 2.0 and 8.0 × 10¹⁶ ions/cm² in the annealing process. The phenomena described above can be attributed to differences in defect formation in the specimens.     

The change in the hardness of LCAC, TZM, and ODS molybdenum in the post-irradiated and annealed conditions

Hardness measurements were performed on wrought Low Carbon Arc Cast (LCAC), TZM, and Oxide Dispersion Strengthened (ODS) molybdenum in the post-irradiated and post-irradiated + annealed condition to determine the recovery kinetics. Irradiations performed in the High Flux Isotope Reactor (HFIR) at nominally 300 °C and 600 °C to neutron fluence levels that range from 10.5 to 246 × 10²⁴ n/m² (E > 0.1 MeV) resulted in relatively large increases in hardness (77-109%), while small increases in hardness (<18%) were observed for irradiations at 870-1100 °C. The hardness recovery for ODS and LCAC irradiated at 300 °C and 600 °C were shown to be complete at 980 °C and ≈ 1100-1250 °C, respectively. Isothermal annealing at 700 °C was used to determine the activation energy for recovery of LCAC and ODS (3.70-4.88 eV ± 0.28-0.77 eV), which is comparable to values reported in the literature for molybdenum vacancy self-diffusion. This suggests that recovery of LCAC and ODS is controlled by the solid-state diffusion of vacancies in the bulk, and that the finer grain size and particle size ODS does not affect this mechanism. TZM exhibited slower recovery kinetics, which can be explained by the solute atoms (titanium and zirconium) inhibiting vacancy diffusion.     

Temperature dependence of He trapping in niobium

The total amount and the depth distributions of 9 and 15 keV implanted ³He ions trapped in polycrystalline niobium have been studied using the ³He(d,p)⁴He reaction. The implantation target temperature was varied from 20 to 1000° C and subsequent anneal studies were carried out for temperatures up to 1600° C. For implantation temperatures below 400° C all ²He particles coming to rest in the target are trapped. Between 500°C and 1000°C the trapping probability decreases gradually with increasing temperature to a few percent. A greater amount of helium is always retained upon annealing of a lower temperature implant to a particular temperature than is retained for implantation at that temperature.     

Surface exfoliation and defect structures in Si induced by 160 keV He and 110 keV H ion implantation

Cz n-type Si(100) wafers were implanted at room temperature with 160 keV He ions at a fluence of 5 × 10¹⁶/cm² and 110 keV H ions at a fluence of 1 × 10¹⁶/cm², singly or in combination. Surface phenomena and defect microstructures have been studied by various techniques, including scanning electron microscopy (SEM), atomic force microscopy (AFM) and cross-sectional transmission electron microscopy (XTEM). Surface exfoliation and flaking phenomena were only observed on silicon by successive implantation of He and H ions after subsequent annealing at temperatures above 400 °C. The surface phenomena show strong dependence on the thermal budget. At annealing temperatures ranging from 500 to 700 °C, craters with size of about 10 μm were produced throughout the silicon surface. As increasing temperature to 800 °C, most of the implanted layer was sheared, leaving structures like islands on the surface. AFM observations have demonstrated that the implanted layer is mainly transfered at the depth around 960 nm, which is quite consistent with the range of the ions. XTEM observations have revealed that the additional low fluence H ion implantation could significantly influence thermal growth of He-cavities, which gives rise to a monolayer of cavities surrounded by a large amount of dislocations and strain. The surface exfoliation effects have been tentatively interpreted in combination of AFM and XTEM results.