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.     

RBS analyses of xenon-irradiated Ti and TiN films

TiN films of 30–300 nm thickness, deposited onto stainless steel via magnetron sputtering, and 10 μm thick Ti foils were irradiated with 80–360 keV Xe⁺ ions at influences of φ = 10¹⁵–10¹⁷ ions/cm². The Xe content was depth-profiled by means of 900 keV He⁺⁺ Rutherford backscattering. Irradiations of films with a thickness exceeding the ion range (at 80 and 250 keV) led to saturation effects due to sputtering and outdiffusion from the near-surface region. The sputtering yields deduced at low Xe fluences were compared to calculations for mono-elemental and compound sputtering. Surface blistering was observed after 250 keV saturation implantation into Ti. For TiN layers with a thickness comparable to the ion range, precipitation of the mixing gas at the interface was observed which finally led to the destruction of the layers. The dependence of the Xe fraction accumulated in the interface is discussed in terms of thermal-spike calculations.     

Influence of the surface conditions on permeation in the deuterium–MANET system

The condition of the surfaces is of crucial importance for the deuterium permeation through materials. In this work a study of the surface constants for the adsorption (σk₁) and release (σk₂) of deuterium under different surface conditions on the martensitic steel DIN 1.4914 (MANET) has been carried out. The growth of an oxide surface layer (Cr₂O₃) of about 25–30 nm in a MANET sample, heat treated in an oxidizing environment, compared to the bare MANET that have a ‘natural' oxide of about 5 nm has provoked a reduction of both the permeation rate and the recombination coefficient (about 3 orders of magnitude). In addition, the permeation governing process has changed from diffusion-limited to surface-limited. The measurements of the permeation rate of deuterium were performed by a gas-phase permeation technique over the temperature range 574–746 K and for deuterium driving pressures in the range from 3 to 10⁵ Pa.     

Deuterium permeation of amorphous alumina coating on 316L prepared by MOCVD

The deuterium permeation behavior of the alumina coating on 316L stainless steel prepared by metal organic chemical vapor deposition (MOCVD) was investigated. The alumina coating was also characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM). It was found that the as-prepared coating consisted of amorphous alumina. This alumina coating had a dense, crack-free and homogeneous morphology. Although the alumina coating was amorphous, effective suppression of deuterium permeation was demonstrated. The deuterium permeability of the alumina coating was 51–60 times less than that of the 316L stainless steel and 153–335 times less than that of the referred low activation martensitic steels at 860–960 K.     

氚在真空贮存容器材料中的吸附和渗透行为

研究了贮存氚靶约4 a和20 a的两个316 L不锈钢真空贮存容器(以下简称贮存容器)及其垫片材料对氚的吸附行为,并对氚在贮存容器材料中的渗透速率进行了测量和分析。结果表明,贮存容器外表面氚污染为几十Bq/cm2,不锈钢与陶瓷中吸附的氚活度均为106Bq/g;热解吸至1 273 K过程中,材料中99%的氚释放出来;在解吸出的氚中,陶瓷中的HTO比例高于不锈钢;贮存温度对氚靶贮存容器的渗氚速率有较大影响,夏季约为冬季的4倍。上述结果提示,氚在贮存容器材料内表面吸附后,一部分会向晶格扩散并滞留下来;另一部分则透过材料向外环境渗透,其中温度是影响氚向外环境渗透的主要因素之一。     

The Study of Surface Properties of Tokamak First Wall Using TiN Coated on Stainless Steel

Structural properties of the synthesized TiN thin film on 316L stainless steel (S.S.316L) were studied to determine its potential application as a protective layer for first wall of Tokamaks. For this purpose we deposited TiN on stainless steel 316L (TiN/S.S.316L) via DC magnetron sputtering method and annealing at 700 °C. Before and after exposure, samples were analyzed by using scanning electron microscopy (SEM), X-ray diffraction (XRD) and a spectrophotometer. The XRD analysis for studying crystalline structure of samples shows the position and intensity of XRD peaks has changed after exposing to 500 shots of Tokamak. It was found that the S.S.316L sample was severely damaged, its reflection dropped significantly but the SEM images show that plasma exposure has not created any cracks and lines on the surface of the TiN/S.S.316L sample and mass of dust particle has been assembled in some area of the sample.     

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.     

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.     

Simulation of thermal stress in Er2O3 and Al2O3 tritium penetration barriers by finite-element analysis

The physical vapor deposition method is an effective way to deposit Al2O3 and Er2O3 on 316L stainless steel substrates acting as tritium permeation barriers in a fusion reactor.The distribution of residual thermal stress is calculated both in Al2O3 and Er2O3 coating systems with planar and rough substrates using finite element analysis.The parameters influencing the thermal stress in the sputter process are analyzed,such as coating and substrate properties,temperature and Young's modulus.This work shows that the thermal stress in Al2O3 and Er2O3 coating systems exhibit a linear relationship with substrate thickness,temperature and Young's modulus.However,this relationship is inversed with coating thickness.In addition,the rough substrate surface can increase the thermal stress in the process of coating deposition.The adhesive strength between the coating and the substrate is evaluated by the shear stress.Due to the higher compressive shear stress,the Al2O3 coating has a better adhesive strength with a 316L stainless steel substrate than the Er2O3 coating.Furthermore,the analysis shows that it is a useful way to improve adhesive strength with increasing interface roughness.     

Mechanism of dynamic strain aging and characterization of its effect on the low-cycle fatigue behavior in type 316L stainless steel

Low-cycle fatigue tests were carried out in air in a wide temperature range from 20 to 650 °C with strain rates of 3.2 × 10⁻⁵–1 × 10⁻² s⁻¹ for type 316L stainless steel to investigate dynamic strain aging (DSA) effect on the fatigue resistance. The regime of DSA was evaluated using the anomalies associated with DSA and was in the temperature range of 250–550 °C at a strain rate of 1 × 10⁻⁴ s⁻¹, in 250–600 °C at 1 × 10⁻³ s⁻¹, and in 250–650 °C at 1 × 10⁻² s⁻¹. The activation energies for each type of serration were about 0.57–0.74 times those for lattice diffusion indicating that a mechanism other than lattice diffusion is involved. It seems to be reasonable to infer that DSA is caused by the pipe diffusion of solute atoms through the dislocation core. Dynamic strain aging reduced the crack initiation and propagation life by way of multiple crack initiation, which comes from the DSA-induced inhomogeneity of deformation, and rapid crack propagation due to the DSA-induced hardening, respectively.     

Effect of Cr2O3 nanosheet insertion on the deuterium permeation behavior of a Cr-Zr-O coating

In this study, a Cr₂O₃ nanosheet (Cr₂O₃ NS) inserted Cr-Zr-O coating was developed as a hydrogen isotope permeation barrier. The Cr₂O₃ NSs, fabricated by rapid heat treatment, were amorphous with a thickness of only several nanometers. These Cr₂O₃ NSs were then incorporated into a Cr-Zr-O multi-metal oxide composite coating via a dip-coating method to form a coating. The effect of the Cr₂O₃ NS concentration on the morphology, microstructure and deuterium permeation resistance of the coating was studied. With the addition of 1.0 g l−1 Cr₂O₃ NSs, compared with the Cr-Zr-O coating without NSs, the permeation reduction factor of the resultant coating was enhanced from 249 °C to 575 °C at 500 °C. The coating, with a thickness of nearly 193 nm, achieved a comparable deuterium resistance that was above two orders of magnitude higher than the steel substrate. The results show that ceramic NSs can serve as effective fillers for enhancing the coating performance when functioning as a hydrogen isotope barrier.     

Study of basic mechanisms of semiconductor devices using ion beam induced charge (IBIC) collection

A change of wave form of current transients induced by a single heavy ion was investigated around a pn junction with 8 μm width and 10 μm length as a function of the ion incident position. Three pn junctions were made on a 3 μm thick Si epilayer (1 × 10¹⁶/cm³) grown on Si substrate and were in a line along an aluminum electrode with 10 μm spacing between the adjacent junctions. The elements of a pn junction array were irradiated with a 1 μm diameter 15 MeV C⁺ heavy ion microbeam spacing steps by 3 μm. At a bias voltage of − 10 V, 148, 91, and 54 fC were collected at the pn junction center, and at 3 μm and 4 μm from the edge of the electrode, respectively. Internal device structure was examined by IBIC (ion beam induced current) method by using a 2 MeV He⁺ ion microbeam. From the IBIC spectrum and the IBIC image, the charge collected from the open space by the diffusion process was observed in addition to the charge collected from the depletion layer of the pn junction.     

Electron beam simulation of disruptions into stainless steel

The effects of repetitive pulsed heating and melt layer formation on type 304 stainless steel are reported. A line-source electron beam with pulse times of 0.5 or 1.5 ms and power densities up to 100 kW/cm² has been used for 1–40 pulse cycles at 500°C substrate temperatures. Numerical calculations of the temperature profiles and their time evolution during melt layer formation are also carried out. Significant metallurgical changes are observed, both in the melt layers and in the adjacent heat-affected zone. Melt depths (10–20 μm) are consistent with calculations and the resolidified regions exhibit columnar or columnar-dendritic microstructure. Appreciable lateral motion within the molten layer results in very rough surfaces and localized cracking occurs. Extensive slip deformation is seen in the adjacent heat-affected zone, and low-cycle fatigue crack initiation is observed after only 20 pulses. Chemical changes in the stainless steel melt layer result from the preferential vaporization of Mn from the melt layer and correlate with the time in the liquid phase. We suggest that the preferential loss of high vapor pressure species such as Mn in the early phases of plasma device operation might provide a unique signature of the impurity introduction mechanism. Disruption melted compositions are distinctly different from the more-nearly stochiometric ratios of Mn/Cr/Ni expected for sputter erosion.     

高温水中氯离子对316L不锈钢应力腐蚀裂纹扩展速率的影响

本文采用直流电压降(DCPD)方法,使用恒K(K=27.5 MPa·m1/2)加载方式,在核电厂高温高压水环境中研究了氯离子对316L不锈钢的应力腐蚀裂纹扩展速率的影响。实验结果表明:在高温除氧水中,氯离子会加快316L不锈钢的应力腐蚀裂纹扩展速率,且当水中存在溶解氧时,氯离子对应力腐蚀裂纹扩展速率的影响更明显。     

Corrosion of steels with surface treatment and Al-alloying by GESA exposed in lead–bismuth

Corrosion tests were performed for T91, E911 and ODS (oxide dispersion strengthened) with surface treatment and Al-alloying by pulsed electron beam (GESA—GepulsteElektronenStrahlAnlage) in flowing lead bismuth eutectic (LBE) with an oxygen content of 10⁻⁶ wt% at 550 °C for 2000 h. The result was that the surface treatment by GESA led to a faster growing multiphase oxide layer which was very homogenous in thickness. After exposure of specimens to LBE, the average oxide layer at the surface was 14–15 μm thick for ODS, 19–20 μm for E911 and 8–22 μm for T91. No dissolution attack occurred. On the surface of the Al-alloyed specimens, thin protective alumina layers were observed at the places where FeAl was formed by the GESA process, otherwise multiphase oxide layers or corrosion attack were observed.     

Helium dilution effect on hydrogen permeation in 316L stainless steel and nickel-base heat-resistant alloys

Effects of inert-gas dilution on hydrogen permeation have been investigated in 316L stainless steel, Inconel 600, Inconel 750, Nimonic 80A and Hastelloy X at 1173 K and 1073 K, by employing a gas-flow system. We used gas mixtures of hydrogen and helium, whose hydrogen concentration ranged from 10^?5 to 10^?1. For the steady-state permeation, the dilution of hydrogen caused no anomalous effects and the permeation rate conformed to Sieverts' law. However, for the transient state, the hydrogen permeation was retarded by the dilution with helium. The retardation effect is discussed in terms of an adsorption model and explained by a decrease in sticking probability at the alloy surface with the dissociative adsorption of hydrogen.     

On the use of MWCVD diamond as thermoluminescent gamma dosimeter

The thermoluminescence (TL) characterization of microwave plasma assisted chemical vapor deposition diamond (MWCVD) films of 6 and 12 μm thickness grown on (1 0 0) silicon substrates was performed. The films exhibited a single well-resolved TL peak around 580 K at doses lower than 40 Gy. As the irradiation dose increased the TL peak broaden and shifted towards the low temperature side of the glow curve. The diamond samples exposed to 0.67 Gy/min ⁶⁰Co gamma radiation displayed a linear dose behavior up to 100 Gy being non-linear for higher doses. The 12 μm film showed lower TL efficiency as compared to the 6 μm specimen. The discrepancy was attributed to the non-uniform distribution of nucleated sp³ diamond and sp² bonded carbon on the substrate as revealed by SEM micrograph and Raman spectroscopy of the samples. The integrated TL glow curve of the samples exhibited low room temperature thermal fading and 3% reproducibility. The results show that MWCVD diamond films possess promising properties for radiation dosimetry applications.     

Research of Si and GaAs diode structures by Ion Beam Induced Charge (IBIC) collection

A Si pn junction diode and a GaAs Schottky diode were prepared for studying the basic mechanism of charge collection followed by high energy charged particle incidence in order to improve the resistance against single event upset. A 2 μm wide and 20 μm long rectangular Al electrode attached to a circular Al electrode with a 50 μm diameter was made on a 2.5 μm thick epilayer (minority carrier density 2 × 10¹⁵ /cm³). Both a Schottky electrode of Al (5 μm × 110 μm) and two ohmic electrodes of AuGe/Ni (110 μm × 110 μm) were made on a 2 μm thick epilayer (7.3 × 10¹⁵ /cm³) grown on a semi insulator GaAs substrate (1 × 10⁷ Ω cm). The internal device structure was examined by the IBIC (Ion Beam Induced Charge) method using a 2 MeV He⁺ ion microbeam. IBIC images clearly show an Al electrode, the SiO₂, and an epilayer. These results were then used to improve the qualities of the test diodes.     

不锈钢和铜吸氚及其干法去污

为了对不锈钢和无氧铜吸氚后氚在其内部的分布情况及除氚去污方法进行研究,对模拟吸氚及加热去污后的样品进行了酸蚀刻以考察氚在金属层中的分布情况;单独加热或加热结合通入空气、O3和紫外线(UV)进行去污,考察不同去污方式的去污效果。结果表明:金属在表层1μm内吸附了大量的氚,约占总量的42%;加热到500℃及联合去污不锈钢的最佳去污因子达到286,铜为150,通入气体在中温条件下对金属去污最有效,加热是金属去污最有效方式;氚热解吸形态分析表明氚污染不锈钢有4种吸附态。     

Deuterium Retention and Physical Sputtering of Low Activation Ferritic Steel

Low activation materials have to be developed toward fusion demonstration reactors. Ferritic steel, vanadium alloy and SiC/SiC composite are candidate materials of the first wall, vacuum vessel and blanket components, respectively. Although changes of mechanical-thermal properties owing to neutron irradiation have been investigated so far, there is little data for the plasma material interactions, such as fuel hydrogen retention and erosion. In the present study, deuterium retention and physical sputtering of low activation ferritic steel, F82H, were investigated by using deuterium ion irradiation apparatus. After a ferritic steel sample was irradiated by 1.7 keV D^ ions, the weight loss was measured to obtain the physical sputtering yield. The sputtering yield was 0.04, comparable to that of stainless steel. In order to obtain the retained amount of deuterium, technique of thermal desorption spectroscopy (TDS) was employed to the irradiated sample. The retained deuterium desorbed at temperature ranging from 450 K to 700 K, in the forms of DHO, D2, D2O and hydrocarbons. Hence, the deuterium retained can be reduced by baking with a relatively low temperature. The fiuence dependence of retained amount of deuterium was measured by changing the ion fiuence. In the ferritic steel without mechanical polish, the retained amount was large even when the fluence was low. In such a case, a large amount of deuterium was trapped in the surface oxide layer containing O and C. When the fluence was large, the thickness of surface oxide layer was reduced by the ion sputtering, and then the retained amount in the oxide layer decreased. In the case of a high fluence, the retained amount of deuterium became comparable to that of ferritic steel with mechanical polish or SS 316 L, and one order of magnitude smaller than that of graphite. When the ferritic steel is used, it is required to remove the surface oxide layer for reduction of fuel hydrogen retention. Ferritic steel sample was exposed to the environment of JFT-2M tokamak in JAERI and after that the deuterium retention was examined. The result was roughly the same as the case of deuterium ion irradiation experiment.