Study on the Chemical Compatibility Study Between Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript> Pebbles and 14Cr-ODS Steel

In order to investigate the chemical compatibility between tritium breeder Li₂TiO₃ pebbles and tritium breeder blanket material oxide dispersion strengthened (ODS) steel, the contact interface between Li₂TiO₃ pebbles and ODS steel heated in argon atmosphere at 500, 600 and 700 °C for 300 h was studied. It was found that the ions of pebbles could diffuse and corrode with the cladding material after a long-time reaction at high temperature. The corrosion area formed on the surface of Li₂TiO₃ pebbles was small. With the increase of temperature, a zone with enriched iron was found on the surface of the pebble. This part of the surface was the direct contact surface between the pebble and the steel. At the same time, the relative density of the pebbles increased and the crush load was decreased to 30 N. In addition, a slight corrosion phenomenon was found on the surface of ODS steel. It has been proved that the main components of the corrosion products were the complex oxide containing Fe and Cr and the complex oxide containing Li and Fe.     

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.     

我国聚变堆结构材料表面阻氚涂层的研究进展

阻氚涂层是聚变堆实现氚自持及氚安全的关键科学与技术问题之一。我国通过国家磁约束聚变能发展研究专项依托国内优势单位部署了阻氚涂层基础问题及工程化技术研发工作。本文介绍了国内外聚变堆结构材料表面阻氚涂层研究进展,重点评述了近几年我国在阻氚涂层的材料选择、制备技术及阻滞氢渗透机制三个科学技术问题的研究进展,提出今后的研究方向。目前我国阻氚涂层材料类型以氧化物涂层为主,涂层制备工艺技术在不断优化和更新。Al2O3/FeAl阻氚涂层的电化学沉积铝(ECA)、粉末包埋渗铝(PC)及热浸铝(HDA)等方法的工艺处理规模及涂层阻氚性能在国际上均相对领先。发展了研究阻氚涂层阻滞氢渗透作用机理的方法,将通常基于Fick定律的表象研究方法向原子级方法前推了一步。未来需在考虑涂层制备工艺与基体材料成分、性能的关系及其在复杂形状结构件的适用性基础上,开发长寿命、高阻氚性能的阻氚涂层材料及制备工艺。     

Microstructure characterization of oxidation of aluminized coating prepared by a combined process

Alumina layer is a good candidate for the tritium penetration barrier that is important in the control of tritium losses due to permeation through structural materials used in high-temperature gas-cooled reactors and in fusion reactors. This paper describes the microstructure of the oxide film of the tritium penetration barrier formed on 316L stainless steel, which was prepared by a combined process, namely, aluminizing and oxidizing treatments using a double glow plasma technology. Microstructure and phase structure of the coatings investigated were examined by scanning electronic microscope (SEM), X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM), respectively. The chemical composition and the chemical states of Al, O elements in the oxidation film were identified by X-ray photoelectron spectroscopy (XPS). After aluminization, the typical microstructure of the coating mainly consisted of an outer high aluminum-containing intermetallic compound layer (Fe₂Al₅ and FeAl) and intermediate ferritic stainless steel (α Fe(Al))layer followed by the austenitic substrate. After the combined process, an oxide layer that consisted of Al₂O₃ and spinel FeAl₂O₄ had been successfully formed on the aluminizing coating surface, with an amorphous outmost surface and an underlying subsurface nanocrystalline structure.     

Reaction Kinetics for the Synthesis of Li<Subscript>4</Subscript>SiO<Subscript>4</Subscript> by Solid State Reaction from Li<Subscript>2</Subscript>SiO<Subscript>3</Subscript> and Li<Subscript>2</Subscript>CO<Subscript>3</Subscript> for Tritium Breeder

Currently, Li₄SiO₄ has been considered one of the best candidates for tritium breeders. Besides, it has also been suggested to be the promising high-temperature carbon dioxide (CO₂) solid sorbent and lithium ion conducting material. As the knowledge of reaction kinetics can offer either a practical or theoretical purpose for predicting and optimizing the reaction process, the kinetics of formation of Li₄SiO₄ from Li₂CO₃ and Li₂SiO₃ were investigated by non-isothermal thermogravimetric technique at four different heating rates. The Malek method results showed that the reaction was the Avarami–Erofeev model, i.e., at about 650 °C the Li₂SiO₃ and Li₂CO₃ with molar ratio of 1:1 formed Li₄SiO₄ crystal nucleus randomly, and then it grew by the diffusion of Li and O through Li₄SiO₄ layer. And the diffusion stage was the rate controlling step. The performances of Li₄SiO₄ pebbles fabricated by a graphite bed process using Li₂SiO₃ and Li₂CO₃ were also evaluated.     

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.     

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.     

A Measurement Platform Scheme and Data Post-processing Method for Thermal Conductivity of Li<Subscript>4</Subscript>SiO<Subscript>4</Subscript> Pebble Bed

The effective thermal conductivity of tritium breeder pebble bed is an important thermal parameter and must be known for the thermo-mechanical design of solid tritium breeder blankets. In order to obtain the parameter, experimental measurement is an effective method. A measurement platform was designed by University of Science and Technology of China for CFETR solid blanket scheme to measure the immediate thermal conductivity data and study the effect of pebble bed temperature, the purge gas pressure and pebble deformation on the thermal conductivity of pebble bed. Measurements were performed based on about 1 mm diameter Li₄SiO₄ pebbles in the temperature range between 100 and 800 °C, with purge gas pressure ranging from 0.1 to 0.3 MPa. This paper described a measurement platform scheme by thermal probe method. On the other hand, for the sake of increasing the precision of thermal conductivity data transformed from temperature data, some improvements for the data post-processing using Monte Carlo inversion method were made in this paper too.     

Characterization of Chemical Densified Coating as Tritium Permeation Barrier

In a fusion blanket design, ceramic coating on structural materials has been considered to be used as a tritium permeation barrier. The Chemical Densified Coating (CDC) method has some advantage compared with another coating method. This method is capable to form densified coating on either the outer or the inner surface of a tube or a container. This process temperature is low (450°C). The fabrication technique of Cr₂O₃-SiO₂ coating had been developed using CDC method. However, Cr₂O₃-SiO₂ coating had open pores in the coating. For filling open pores, the densification treatment by CrPO₄ was examined. In this study, the verification of open pores, the thermal shock resistivity, the adhesion strength and the deuterium permeability were evaluated and compared with Cr₂O₃-SiO₂ (Type 1) coating and Cr₂O₃-SiO₂ including CrPO₄ (Type 2) coating. From these results, it was confirmed that Type 2 coating had a good adhesion property, and permeation reduction factor of SS316 with Cr₂O₃-SiO₂ including CrPO₄ coating reached about 1,000 at 600°C.     

Micro-XRF and micro-XAFS studies of an Al matrix Fe–Ni composite

We report on the distribution and local coordination of Fe and Ni in an Al matrix Fe–Ni composite, by means of X-ray Fluorescence mapping (XRF), micro- (μ-) and conventional Extended X-ray Absorption Fine Structure (EXAFS) spectroscopies. The μ-XRF maps reveal that Fe segregates and forms Fe-rich islands which are depleted of Ni. The combined μ-EXAFS and EXAFS results reveal that both metals are bonded only to Al. More specifically, the Fe-rich islands are identified as FeAl₃ microcrystallites while in the Fe-poor regions, Fe belongs to an intermetallic FeAl phase. The bonding environment of Ni is also modified due to the variations in the distribution of the metals. In the region with high Ni concentration, i.e. Fe-poor regions, the Ni atoms are bonded to 10.5 ± 1.1 Al atoms that substitute Ni in fcc Ni. On the contrary, in the Ni-poor regions, where the Fe concentration exhibits maxima, the number of Al atoms in the first nearest shell of Ni is equal to 7.8 ± 0.9, i.e. in this region, Ni forms intermetallic NiAl. Finally, the atomic percentage of the Fe and Ni atoms that belong to the Fe-rich and Fe-poor islands is determined from the Fe-K and Ni-K edge EXAFS analysis. The majority of the Fe atoms (～80 at%) belongs to the FeAl₃ microcrystallites, embedded into a FeAl matrix. On the contrary, the same atomic percentage of Ni atoms (～50 at%), occupies sites in both the NiAl regions as well as in the matrix of the (Ni, Al) solid solution.     

Corrosion behavior of Al-surface-treated steels in liquid Pb-Bi in a pot

Corrosion tests were performed in oxygen-saturated liquid Pb-Bi at 450 °C and 550 °C in a pot for 3000 h for Al-surface-treated steels containing various levels of Cr contents. The Al surface treatments were achieved using a gas diffusion method and a melt dipping method. Al₂O₃, FeAl₂ and AlCr₂ produced by the gas diffusion method exhibited corrosion resistance to liquid Pb-Bi, while the surface layer produced by the melt dipping method suffered a severe corrosion attack. Fe₄Al₁₃ and Fe₂Al₅ produced by the melt dipping method disappeared during the corrosion test at 550 °C and only FeAl remained.     

Metallurgical characterizations of Fe–Cr–Ni–Zr base alloys developed for geological disposal of radioactive hulls

Alloy melting route is currently being considered for radioactive hulls immobilization. Towards this, wide range of alloys, belonging to Zirconium–Iron binary and Zirconium–Stainless steel pseudo-binary systems have been prepared through vacuum arc melting route. Detail microstructural characterization and quantitative phase analyses of these alloys along with interaction study between Zirconium and Stainless steel coupons at elevated temperatures identify Zr(Fe,Cr)₂, Zr(Fe,Cr), Zr₂(Fe,Cr), Zr₃(Fe,Ni), Zr₃(Fe,Cr), Zr₃(Fe,Cr,Ni), β-Zr and α-Zr as the most commonly occurring phases within the system for Zirconium rich bulk compositions. Nano-indentation studies found Zr(Fe,Cr)₂ and Zr(Fe,Cr) as extremely hard, Zr₃(Fe,Ni) as moderately ductile and β-Zr, Zr₂(Fe,Cr) as most ductile ones among the phases present. Steam oxidation studies of the alloys, based on weight gain/loss procedure and microstructural characterization of the mixed oxide layers, suggest that each of the alloys responded to the corrosive environment differently. Fe₂O₃, NiFe₂O₄, NiO, monoclinic ZrO₂ and tetragonal ZrO₂ are found to be most common constituents of the oxide layers developed on the alloys. Integrating the microstructural, mechanical and corrosion properties, ZrFeCrNi3 (Zr: 84.00, Fe: 11.20, Cr: 3.20, Ni: 1.60, in wt.%) is identified as the acceptable base alloy for disposal of radioactive hulls.     

Effect of CH<Subscript>4</Subscript> Ion Implantation in Pure Aluminium

In this paper, aluminium samples with 99.96% purity were exposed to ion beam, extracted from CH₄ plasma. Implantation of ions were performed for 50 keV energy and various doses ranging from 1 × 10¹⁷ to 6 × 10¹⁷ ions/cm². Morphology of surfaces, roughness and its evolution during variation of ion dose has been studied by atomic force microscopy (AFM). Microstructure of the modified surfaces after ion implantation has been obtained by X-ray diffraction technique and Raman spectroscopy. Formation of aluminium carbide (Al₄C₃) was confirmed by XRD results at implantation doses of 3 × 10¹⁷ and 6 × 10¹⁷ ions/cm². In addition, it was observed that when the ion dose is increased, orientation of aluminium planes change from (2 2 0) to (2 0 0). Corrosion test was performed and compared for implanted and un-implanted samples. The results showed that corrosion resistivity increase by accumulation of ion dose.     

Analysis of Tritium Behavior in Very High Temperature Gas-Cooled Reactor Coupled with Thermochemical Iodine-Sulfur Process for Hydrogen Production

The tritium concentration in the hydrogen product in Japan's future very high temperature gas-cooled reactor (VHTR) system coupled with a thermochemical water-splitting iodine-sulfur (IS) process (VHTRIS system), named GTHTR300C, was estimated by numerical analysis. The tritium concentration in the hydrogen product significantly depended on undetermined parameters, i.e., the permeabilities of a SO₃ decomposer and a H₂SO₄vaporizer made of SiC. Thus, the estimated tritium concentration in the hydrogen product for the conservative analytical condition ranged from 3.4 × 10^?3 Bq/cm³ at STP (38 Bq/g-H₂) to 0.18 Bq/cm³ at STP (2,000 Bq/g-H₂). By considering the tritium retained by core graphite and the reduction in permeation rate by an oxide film on the heat transfer tube of the IHX and the HI decomposer, the tritium concentration in the hydrogen product decreased to the range from 3.3 × 10^?5 Bq/cm³ at STP (0.36 Bq/g-H₂) to 5.6 × 10^?3 Bq/cm³ at STP (63 Bq/g-H₂), which were smaller than those for the conservative analytical condition by factors of about 3.2 × 10^?2 and 9.6 × 10^?3, respectively. The effectof the helium flow rate in the helium purification system on the tritium concentration in the hydrogen product was also evaluated.     

Formation of diffusion barrier coating on superalloy 690 substrate and its stability in borosilicate melt at elevated temperature

Aluminized and thermally oxidized superalloy 690 substrates forming Al₂O₃ layer on (NiCr)Al + Cr₅Al₈ types aluminides and bare substrates were exposed in sodium borosilicate melt at 1248 K for 192 h. SEM–EDXS analysis along the cross-section of bare substrate with adhered glass revealed formation of a continuous, thick Cr₂O₃ layer at the substrate/glass interface due to its low solubility in borosilicate melt. XRD on aluminide coated and thermally oxidized specimen revealed existence of Al₂O₃ along with NiAl and Cr₅Al₈ type phases after the exposure in borosilicate melt. SEM–EDXS analysis along the cross-section of aluminide coated and thermally oxidized sample with adhered glass indicated good stability of coating in borosilicate melt without any phase formation at the coating/glass interface. However, some Al enrichment in glass phase adjacent to interface was noticed without any significant Ni or Cr enrichment.     

Effect of Low Pressure Nitrogen–Oxygen (N<Subscript>2</Subscript>/O<Subscript>2</Subscript>) Plasma Treatment on Surface Properties of Polypropylene Films

In this paper the effect of plasma treatment by using mixed gas (N₂/O₂) on surface properties of a Polypropylene PP films were investigated as a function of O₂ content and treatment time. Results obtained by using Fourier Transform infrared spectrometer (FTIR), contact angle measurement and scanning electron microscopy (SEM). It is found that plasma treatment can change chemical structure of polymer surfaces partially. SEM images revealed distinct changes in topography of PP due to O₂/N₂ plasma treatment. Finally wettability and surface energy before and after treatment investigated in different conditions.     

Characterization of solidified melt among materials of UO2 fuel and B4C control blade

To predict the fundamental phase relationships in the solidified core melt of the Fukushima Daiichi Nuclear Power Plant, solidified melt samples of the various core materials [B₄C, stainless steel, Zr, ZrO₂, (U,Zr)O₂] were prepared by arc melting. Phases and compositions in the samples were determined by means of X-ray diffraction, microscopy, and elemental analysis. With various compositions, the only oxide phase formed was (U,Zr)O₂. After annealing, the stable metallic phases were an Fe-Cr-Ni alloy and an Fe₂Zr-type (Fe,Cr,Ni)₂(Zr,U) intermetallic compound. The borides, ZrB₂ and Fe₂B-type (Fe,Cr,Ni)₂B, were solidified in the metallic part. Annealing at 1773 K under an oxidizing atmosphere (Ar-0.1%O₂) resulted in the oxidation of U and Zr in the alloy and in ZrB₂, and consequently the (Fe,Cr,Ni)₂B and Fe-Cr-Ni alloy became dominant in the metallic part. The experimental phase relationships in the metallic part agreed reasonably with the thermodynamic evaluation of equilibrium phases in a simplified B₄C–Fe–Zr system. The metallic Zr content in the melt was found to be a key factor in determining the phase relationships. As a basic mechanical property, the microhardness of each phase was measured. The borides, especially ZrB₂, showed notably higher hardness than any other oxide or metallic phases.     

Effect of O<Subscript>2</Subscript>/Ar Mixture on the Structural and Optical Properties of ZnO Thin Films Fabricated by DC Cylindrical Magnetron Sputtering

Direct Current Cylindrical Magnetron Sputtering Setup was used to deposit ZnO thin films on BK7 substrates. The effects of changing O₂/Ar reactive gas mixtures on the structural and optical properties of films were studied. Crystallinity and structure of films were obtained by X-ray diffraction (XRD). Preferential crystalline growth orientation of ZnO films detected by XRD was always along the (002) orientation. The thickness of films was measured by surface profilometer which showed thickness increasing from 68.7 to 80.8 nm for 3–6% O₂ amount respectively. The morphology and roughness of the films were investigated by Atomic Force Microscopy (AFM). As oxygen gas amount was increased, the roughness and the grain size were decreased and the deposition rate was increased. The optical transmittance of ZnO films are obviously affected by the changing of O₂/Ar reactive gas mixtures. All films exhibit a transmittance higher than 70% in the visible region. The optical band gap of films was measured by Tauc’s method. The results show that by increasing the amount of O₂ in reactive gas mixture, the optical band gap of deposited films increases.     

Al2O3/Y2O3/ZrO2 Ceramic Composite Properties Investigation by Plasma Focus Device

The Al₂O₃–Y₂O₃–ZrO₂ eutectic composition samples were prepared using the Al₂O₃, Y₂O₃, ZrO₂ powder treated at 900 °C for 30 min, pressed at 5 ton for 15 s and sintered at 1500 °C for 2 h. The locally made dense plasma focus (DPF) system with energy 2.8 kJ was used to surface modification of these samples. The samples, mounted at distance about 2 cm from the anode, were exposed to three shots of the DPF in Ar gas at a pressure of 0.8 mbar. The phase and elemental analysis of the untreated and plasma treated samples were conducted by the Raman and EDX spectroscopy. The Raman spectroscopy showed the formation of new phases (α-Al₂O₃ and c-ZrO₂) in the treated samples. The micro-hardness of the plasma treated samples was increased by about 280 % in comparison with the untreated sample.     

Production de defauts dans des films de fer; etude en fonction de la densite d'energie deposee dans les cascades

Oxidation of SUS-316 stainless steel for a fast breeder reactor fuel cladding was examined in the temperature range of 843–1010 K under the oxygen pressure of 1017 t – 10 t-13 Pa hy use of an experimental technique of a Ni/NiO oxygen buffer. The formation of the duplex oxide layer, i.e. an outer Fe₃O₄ layer and an inner (Fe, Cr, Ni)-spinel layer, was observed and the oxidation kinetics was found to obey the parabolic rate law. The oxygen pressure and temperature dependence of the parabolic rate constant k_p(P_O2,T) was determined as follows: k_p(P_O2,T)/kg² · m^?1 · s^?1 = 0.170(P_O2/Pa)^0.141exp[?114 × 10³/(RT/J)]. On the basis of the oxidation kinetics and the metallographic information, the outward diffusion of Fe in the outer oxide layer was assigned to be the rate-determining process.