Preparation of Cr2O3 film by MOCVD as hydrogen permeation barrier

Cr₂O₃ film on structural material as hydrogen permeation barrier can be applied in many areas such as hydrogen storage devices, vacuum solar receivers and fusion reactors. In this study, the Cr₂O₃ film was prepared by MOCVD on 316L stainless steel using chromium(III) acetylacetonate as precursor. The film was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The hydrogen permeation inhibition performance of films was investigated by deuterium permeation experiment. The 366 nm thick Cr₂O₃ film on 316L could reduce the deuterium permeability by 24–117 times at 823–973 K, revealing efficient inhibition to hydrogen permeation. The Cr₂O₃ film is dense, crack-free and has a corundum structure which possesses a more stable structure than a metastable phase or an amorphous phase. Moreover, the crystalline Cr₂O₃ could be easily obtained by MOCVD at a low temperature, e.g. 773 K.     

Effect of surface oxide layer on deuterium permeation behaviors through a type 316 stainless steel

Effect of surface oxide layer on the hydrogen isotope permeation was studied. Iron oxide was uniformly formed in the oxide layer, although chromium was limited at the interface between the oxide layer and bulk SS-316. The permeation behavior of deuterium for oxidized SS-316 was compared with that for unoxidized SS-316 at temperature range of 333–673 K. The deuterium permeability for the oxidized SS-316 was reduced 1/10–1/20 times as high as that for unoxidized one. However, the activation energy of deuterium permeation as gas form for oxidized SS-316 was almost the same as that for unoxidized SS-316 and was 0.64 eV, which was almost consistent with the sum of activation energies for diffusion and solubility. This fact indicates that the deuterium permeation is diffusion limited. The permeability of deuterium as water form was almost constant even if heating temperature is high, showing that the deuterium was permeated through bulk SS-316 and react with oxygen at the oxide layer as water desorption, which is controlled by the permeation flux of deuterium and oxygen concentration on the surface of oxide layer in downstream side.     

Hydrogen isotope permeation from cooling water through various metal piping

In order to investigate the behavior of hydrogen isotope on the water–metal boundary, deuterium permeation experiments from heavy water vessel through various metal piping, such as pure iron (Fe), nickel (Ni), stainless steel (SS304), and pure iron with 10 μm gold plating, were performed at 573 K and at 15 MPa. During the experiment, surfaces of metal piping except gold plating one were oxidized at the heavy water boundary and then deuterium would generate by the oxidation reactions. This deuterium could be detected by mass spectrometer, which monitored the inside gases of the piping under continuous evacuation. The result showed clearly that the deuterium permeated through Fe, Ni, and SS304 piping was detected as mainly deuterium gas (D₂) under continuous evacuation, though that through gold plating one could not be detected effectively. The D₂ permeation rate through Fe, Ni, and SS304 piping reached equilibrium conditions with oxide generation at D₂O–metal boundary, although concluding the transfer mechanism will require further testing and modeling activities.     

The effect of dose rate on the response of austenitic stainless steels to neutron radiation

Depending on reactor design and component location, austenitic stainless steels may experience significantly different irradiation dose rates in the same reactor. Understanding the effect of dose rate on radiation performance is important to predicting component lifetime. This study examined the effect of dose rate on swelling, grain boundary segregation, and tensile properties in austenitic stainless steels through the examination of components retrieved from the Experimental Breeder Reactor-II (EBR-II) following its shutdown. Annealed 304 stainless steel, stress-relieved 304 stainless steel, 12% cold-worked 316 stainless steel, and 20% cold-worked 316 stainless steel were irradiated over a dose range of 1–56 dpa at temperatures from 371 to 440 °C and dose rates from 0.5 to 5.8 × 10⁻⁷ dpa/s. Density and tensile properties were measured for 304 and 316 stainless steel. Changes in grain boundary composition were examined for 304 stainless steel. Swelling appears to increase at lower dose rates in both 304 and 316 stainless steel, although the effect was not always statistically significant. Grain boundary segregation also appears to increase at lower dose rate in 304 stainless steel. For the range of dose rates examined, no measurable dose rate effect on tensile properties was noted for any of the steels.     

The formation of tritium permeation barriers by CVD

The effectiveness as permeation barriers of the following CVD coatings have been investigated: TiC (1 to 2 μm in thickness); a bi-layer of TiN on TiC (3 μm total thickness) and CVD A1₂O₃ on a TiN/TiC bi-layer. The substrate materials were TZM (a Mo alloy) and 316L stainless steel in the form of discs of diameter 48 mm and thickness 0.1 or 1 mm. Permeation measurements were performed in the temperature range 515–742 K using deuterium at pressures in the range 1–50 kPa. CVD layers were shown to form reasonably effective permeation barriers. At a temperature of 673 K TiC is around 6000 times less permeable to deuterium than 316L stainless steel.     

High temperature deformation and fracture behaviour of 316L stainless steel under high strain rate loading

The high temperature deformation and fracture behaviour of 316L stainless steel under high strain rate loading conditions are investigated by means of a split Hopkinson pressure bar. Impact tests are performed at strain rates ranging from 1 × 10³ s^?1 to 5 × 10³ s^?1 and temperatures between 25 °C and 800 °C. The experimental results indicate that the flow response and fracture characteristics of 316L stainless steel are significantly dependent on the strain rate and temperature. The fracture analysis results indicate that the 316L specimens fail predominantly as the result of intensive localised shearing. Furthermore, it is shown that the flow localisation effect leads to the formation of adiabatic shear bands. The fracture surfaces of the deformed 316L specimens are characterised by a dimple-like structure with knobby features. The knobby features are thought to be the result of a rise in the local temperature to a value greater than the melting point.     

Vacuum plasma-sprayed tungsten on EUROFER and 316L: Results of characterisation and thermal loading tests

Vacuum plasma-spraying (VPS) can be used for the industrial deposition of thick W coatings on actively water-cooled components made of low activation steel or stainless steel. Mock-ups made of martensitic steels, EUROFER and F82H, as well as steel 316L, were coated with 2 mm thick W-VPS layers. The coated materials are candidates for first wall components (ITER and DEMO) receiving moderate heat load of up to 1 MW/m². Mixed tungsten/steel interlayers were applied to reduce the residual and thermal stresses at the substrate–coating interface and to improve the adhesion of the coating. The advantage of this mixed interlayer is that no further (high activation) materials have to be introduced to improve coating adhesion.The characterisation of the W-VPS layers includes the evaluation of the coating microstructure, the measurement of physical and mechanical properties and the metallographical examination before and after heat load tests.Heat load tests with steady state operation up to 2.5 MW/m² and cycling heat loads of 2 MW/m², were successfully completed. They confirm the thermomechanical suitability of industrially manufactured W-VPS coatings for plasma facing first wall components made of steel.     

Fuel hydrogen retention of tungsten and the reduction by inert gas glow discharges

Polycrystalline tungsten was exposed to deuterium glow discharge followed by He, Ne or Ar glow discharge. The amount of retained deuterium in the tungsten was measured using residual gas analysis. The amount of desorbed deuterium during the inert gas glow discharge was also measured. The amount of retained deuterium was 2–3 times larger compared with a case of stainless steel. The ratios of desorbed amount of deuterium by He, Ne and Ar glow discharges were 4.6, 3.1 and 2.9%, respectively. These values were one order of magnitude smaller compared with the case of stainless steel. The inert gas glow discharge is not suitable to reduce the fuel hydrogen retention for tungsten walls. However, the wall baking with a temperature higher than 700 K is suitable to reduce the fuel hydrogen retention. It is also shown that the use of deuterium glow discharge is effective to reduce the in-vessel tritium inventory in fusion reactors through the hydrogen isotope exchange.     

Deuterium permeation behavior of erbium oxide coating on austenitic,ferritic, and ferritic/martensitic steels

Tritium permeation barrier is required in fusion blanket for reduction of loss of fuel and health hazard. In this study, deuterium permeation experiments have been performed on four kinds of steels and erbium oxide coatings fabricated by a filtered arc deposition method. The permeation flux of uncoated samples shows diffusion-limited regime in the temperature range 573–723 K and the permeability is corresponding to literature data. The coated samples deposited at room temperature have been tested at 773 K. It is found that the coatings suppress the deuterium permeation to a close level in spite of different types of steel substrates. In addition, the exponent of the driving pressure slightly changes compared to the uncoated sample. However, the permeation regime is still near diffusion limited.     

An advance process of aluminum rich coating as tritium permeation barrier on 321 steel workpiece

We have proposed an advance three-step process, Al-electroplating in ionic liquid followed by heat treating and selectively oxidation, preparing aluminum rich coating as tritium permeation barrier (TPB). In present work, the advance process was applied to 321 steel workpieces. In the Al-electroplating, pieces were coated by galvanostatic electrodeposition at 20 mA/cm² in aluminum chloride (AlCl₃)–1-ethyl-3-methylimidazolium chloride (EMIC) ionic liquid. The Al coating on those pieces all displayed attractive brightness and well adhered to surface of pieces. Within the aluminizing time from 1 to 30 h, a series of experiments were carried out to aluminize 321 steel pieces with Al 20 μm coating at 700 °C. After heat treated for 8 h, a 30 μm thick aluminized coating on piece appeared homogeneous, free of porosity, and mainly consisted of (Fe, Cr, Ni)Al₂, and then was selectively oxidized in argon gas at 700 °C for 50 h to form Al₂O₃ scale. The finally fabricated aluminum rich coating, without any visible defects, had a double-layered structure consisting of an outer γ-Al₂O₃ layer with thickness of 0.2 μm and inner (Fe, Cr, Ni)Al/(Fe, Cr, Ni)₃Al layer of 50 μm thickness. The deuterium permeation reduction factor, PRF, of piece (Φ 80 × 2, L 150 mm) with such coating increased by 2 orders of magnitude at 600–727 °C. The reproducibility of the process was also showed.     

Preparation and investigation of aluminized coating and subsequent heat treatment on 9Cr–1Mo Grade 91 steel

Iron aluminide inner coating with alumina top layer is being considered as a potential solution for tritium permeation barrier and mitigating MHD pressure drop for liquid metal blanket concepts in the fusion reactor systems. Hot-dip aluminizing with subsequent heat treatment seems to offer a good possibility to produce aluminized coating with alumina top layer. 9Cr–1Mo Grade 91 steel samples were hot dipped in Al melt containing 2.25 wt% of Si at 750 °C for 3 min. Heat treatment was performed at 650, 750 and 950 °C for 5 h; samples were either air cooled or furnace cooled. Coatings have been evaluated by SEM, EDX, X-ray diffraction, microhardness, scratch adhesion and Raman spectroscopy. The thickness of the layers and phases formed were influenced by the heat treatment adopted. Fe₂Al₅ was the major phase present in the samples heat treated at 650/750 °C, whereas FeAl and α-Fe(Al) primarily made up the outer and inner layers respectively in the samples heat treated at 950 °C. Cooling method deployed affected the hardness. Air cooled samples had comparatively higher hardness than furnace cooled samples. The scratch test showed the adhesion for the samples heat treated at 950 °C was much better as compared to the samples heat treated at 650/750 °C. Raman spectroscopy analysis showed the presence of both α-Al₂O₃ and γ-Al₂O₃ on the surface of the samples heat treated at 950 °C, while Fe₃O₄ was present in the furnace cooled sample only.     

Surface chemistry analysis of lithium conditioned NSTX graphite tiles correlated to plasma performance

Lithium wall conditioning in NSTX has resulted in reduced divertor recycling, improved energy confinement, and reduced frequency of edge-localized modes (ELMs), up to the point of complete ELM suppression. NSTX tiles were removed from the vessel following the 2008 campaign and subsequently analyzed using X-ray photoelectron spectroscopy as well as nuclear reaction ion beam analysis. In this paper we relate surface chemistry to deuterium retention/recycling, develop methods for cleaning of passivated NSTX tiles, and explore a method to effectively extract bound deuterium from lithiated graphite. Li–O–D and Li–C–D complexes characteristic of deuterium retention that form during NSTX operations are revealed by sputter cleaning and heating. Heating to ～850 °C desorbed all deuterium complexes observed in the O 1s and C 1s photoelectron energy ranges. Tile locations within approximately ±2.5 cm of the lower vertical/horizontal divertor corner appear to have unused LiO bonds that are not saturated with deuterium, whereas locations immediately outboard of this region indicate high deuterium recycling. X-ray photo electron spectra of a specific NSTX tile with wide ranging lithium coverage indicate that a minimum lithium dose, 100–500 nm equivalent thickness, is required for effective deuterium retention. This threshold is suspected to be highly sensitive to surface morphology. The present analysis may explain why plasma discharges in NSTX continue to benefit from lithium coating thickness beyond the divertor deuterium ion implantation depth, which is nominally <10 nm.     

Prospects of using different clad materials in a material test research reactor – Part 3 – The dynamic behavior

The effects of using different clad materials on the dynamics of a material test research reactor were studied. For this purpose, the aluminum clad of an MTR was replaced separately with stainless steel-316 and zircaloy-4. Simulations were carried out to determine the reactor performance under reactivity insertion and loss-of-flow transients. Nuclear reactor analysis code PARET was employed to carry out these calculations. It was observed that during the fast reactivity insertion transient, Al cladded fuel attained the maximum reactor power of 59.34 MW, while stainless steel-316 cladded attained 48.74 MW and zircaloy-4 cladded attained maximum power of 55.87 MW. During the slow reactivity insertion transient, Al cladded fuel attained the maximum reactor power of 12.38 MW, while stainless steel-316 cladded attained 12.23 MW and zircaloy-4 cladded attained maximum power of 12.34 MW. During the loss-of-flow transients, the reactor power of the stainless steel-316 cladded fuel remained slightly lower than the other two. The fuel temperature of stainless steel-316 and zircaloy-4 cladded fuels remained higher due to poor fuel–clad gap conductance.     

Tritium permeation experiments using reduced activation ferritic/martensitic steel tube and erbium oxide coating

Low concentration tritium permeation experiments have been performed on uncoated F82H and Er₂O₃-coated tubular samples in the framework of the Japan-US TITAN collaborative program. Tritium permeability of the uncoated sample with 1.2 ppm tritium showed one order of magnitude lower than that with 100% deuterium. The permeability of the sample with 40 ppm tritium was more than twice higher than that of 1.2 ppm, indicating a surface contribution at the lower tritium concentration. The Er₂O₃-coated sample showed two orders of magnitude lower permeability than the uncoated sample, and lower permeability than that of the coated plate sample with 100% deuterium. It was also indicated that the memory effect of ion chambers in the primary and secondary circuits was caused by absorption of tritiated water vapor that was generated by isotope exchange reactions between tritium and surface water on the coating.     

Measurement of hydrogen isotope concentration in erbium oxide coatings

Hydrogen isotope concentrations in erbium oxide coatings fabricated by filtered arc deposition and metal–organic decomposition have been investigated using nuclear reaction analysis and secondary ion mass spectroscopy. It was found that the deuterium concentration in the coatings fabricated by filtered arc deposition was 300–500 atomic parts per million, whereas the deuterium concentration in the coating fabricated by metal–organic decomposition was approximately 2.0 × 10⁴ atomic parts per million due to hydrogen trapping by carbon impurities. Deuterium concentrations in the coatings fabricated by filtered arc deposition increased with increasing depth in accordance with the increase of grain boundary area density. An in-plane deuterium distribution of the coating by secondary ion mass spectroscopy proved segregation with a net-like structure, indicating that the deuterium diffused through the grain boundaries.     

Mechanical properties and microstructural investigations of TIG welded 40 mm and 60 mm thick SS 316L samples for fusion reactor vacuum vessel applications

The development of advanced fusion reactors like DEMO will have various challenges in materials and fabrication. The vacuum vessel is important part of the fusion reactor. The double walled design for vacuum vessel with thicker stainless steel material (40–60 mm) has been proposed in the advanced fusion reactors like ITER. Different welding techniques will have to be used for such vacuum vessel development. The required mechanical, structural and other properties of stainless steels have to be maintained in these joining processes of components of various shapes and sizes in the form of plates, ribs, shells, etc. The present paper reports characterization of welding joints of SS316L plates with higher thicknesses like 40 mm and 60 mm, prepared using multi-pass Tungsten Inert Gas (TIG) welding process. The weld quality has been evaluated with non-destructive tests by X-ray radiography and ultrasonic methods. The mechanical properties like tensile, bend tests, Vickers hardness and impact fracture tests have been carried out for the weld samples. Tensile property test results indicate sound weld joints with efficiencies over 100%. Hardening was observed in the weld zone in non-uniform manner. Macro and microstructure studies have been carried out for Base Metal (BM), Heat Affected Zone (HAZ) and Weld Zone (WZ). Scanning Electron Microscopy (SEM) analysis carried out for the impact fractured specimens show ductile fracture. The microstructural study and ferrite number data indicate the presence of high content of delta ferrite in the weld zone as compared to the delta ferrite in base metal.     

Structural and magnetic characterization of plasma ion nitrided layer on 316L stainless steel alloy

In this study, an FeCrNi alloy (316L stainless steel disc) was nitrided in a low-pressure R.F. plasma at 430 °C for 72 min under a gas mixture of 60% N₂–40% H₂. Structural, compositional and magnetic properties of the plasma nitrided layer was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and magnetic force microscopy (MFM). The magnetic behaviour of the nitrided layer was also investigated with a vibrating sample magnetometer (VSM). Combined X-ray diffraction, cross-sectional SEM, AFM and MFM, as well as VSM analyses provide strong evidence for the formation of the γ_N phase, [γ_N-(Fe, Cr, Ni)], with mainly ferromagnetic characteristics. The uniform nature of the γ_N layer is clearly demonstrated by the XRD, cross-sectional SEM and AFM analyses. Based on the AFM and SEM data, the thickness of the γ_N layer is found to be ～6 μm. According to the MFM and VSM analyses, ferromagnetism in the γ_N layer is revealed by the observation of stripe domain structures and the hysteresis loops. The cross-sectional MFM results demonstrate the ferromagnetic γ_N phase distributed across the plasma nitrided layer. The MFM images show variation in the size and form of the magnetic domains from one grain to another.     

New integral experiments for large angle scattering cross section data benchmarking with DT neutron beam at JAEA/FNS

A new integral experiment with a deuteron–triton fusion (DT) neutron beam started in order to validate scattering cross section data. First the DT neutron beam was constructed with a collimator. The performance of the collimator system and the characteristics of the DT neutron beam were measured. Second a new integral experiment for type 316 stainless steel (SS316) was carried out with this DT neutron beam. The DT neutron beam of 3.5 cm in diameter was injected to the front surface center of an SS316 cylindrical assembly. Reaction rates of the ⁹³Nb(n,2n)^92mNb reaction in the assembly were measured with the activation foil method and were calculated with the Monte Carlo transport calculation code. The measurement points were located at three positions, on the center of the beam axis and at 15 cm and 30 cm apart from the axis. The ratio of calculation to experiment of the ⁹³Nb(n,2n)^92mNb reaction rate became smaller than 1 with the distance from the beam axis. Then, the dependency of each reaction rate on scattering angle was calculated. It was proved that at off-axis positions, where C/E is smaller than 1, 90° scattering contribute relatively larger than at on-axis positions and backward scattering made little contribution to the results in this experiment. The reasons of the discrepancy between the measured and calculated data will be investigated.     

Prospects of using different clad materials in a material test research reactor – Part 1 – The kinetic parameters

The kinetic parameters of a material test research reactor using stainless steel-316 and zircaloy-4 as clad were calculated. For this purpose, the aluminum clad of an MTR was replaced separately with stainless steel-316 and zircaloy-4. Calculations were carried out to find the core excess reactivity, neutron flux spectrum, prompt neutron generation time and effective delayed-neutron fraction. Nuclear reactor analysis codes including WIMS-D4 and CITATION were employed to carry out these calculations. It was observed that at the beginning of life, the excess reactivity was maximum at 0.054110 Δk/k when zircaloy-4 was used as clad while it was minimum at ?0.365650 Δk/k when stainless steel-316 was the clad as compared to 0.017945 Δk/k for aluminum. The thermal neutron flux at the mid of the central flux trap increased by 59.9% and 12.5% for stainless steel and zircaloy-4 clads, respectively, from the flux of the original aluminum clad. The prompt neutron generation time was maximum at 45.36 μs when stainless steel-316 was the clad while it was minimum at 44.03 μs for the original aluminum clad. The effective delayed-neutron fraction was maximum at 0.007185 for the original aluminum clad while it was minimum at 0.007078 for stainless steel clad.     

Hydrogen transport and solubility in 316L and 1.4914 steels for fusion reactor applications

Equations are given which describe the permeation rate, diffusivity and solubility of hydrogen over the range 250–600°C at pressures up to 10⁵Pa for the 316L stainless and modified 1.4914 martensitic candidate steels proposed for the construction of the Next European Torus (NET). For heat-treated 316L steel, the permeation rates measured agreed well with previous work and did not vary significantly from specimen to specimen or from batch to batch.

Measurements of the permeation rate of hydrogen and deuterium through the modified 1.4914 steel, believed to be the first made, show that the martensitic steel is significantly more permeable than the austenitic steel, by an order of magnitude at 250°C and a factor of five at 600°C. This difference could make it necessary to use permeation barriers on critical components made from the martensitic steel in order to reduce the tritium permeation rate to acceptable levels.