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.     

Effects of Fe and Cr on corrosion behavior of ZrFeCr alloys in 500 °C steam

A study of the corrosion behaviors of ZrFeCr alloy and the influence of microstructure on corrosion resistance are described by X-ray diffraction and scanning electron microscope in this paper. The results show that several ZrFeCr alloys exhibit protective behavior throughout the test and oxide growth is stable and protective. The best alloy has the composition Zr1.0Fe0.6Cr. Fitting of the weight gain curves for the protective oxide alloys in the region of protective behavior, it showed nearly cubic behavior for the most protective alloys. The Zr1.0Fe0.6Cr has the more laves Zr(Fe,Cr)₂ precipitate in matrix and it has the better corrosion resistance. The Zr0.2Fe0.1Cr has little precipitate, the biggest hydrogen absorption and the worst corrosion resistance. The number of precipitates and the amount of hydrogen absorption in Zr alloy plays an important role on corrosion resistance behaviors in 500 °C/10.3 MPa steam.     

Experimental investigation of the Zr corner of the ternary Zr-Nb-Fe phase diagram

Intermediate phases in the Zr-rich region of the Zr-Nb-Fe system have been investigated by X-ray diffraction, optical and electron microscopy and electron microprobe analysis. The chemical composition ranges covered by the alloys studied here are: (41-97) at.% Zr, (32-0.9) at.% Nb and (0.6-38) at.% Fe. The phases found in this region were: the solid solutions α-Zr and β-Zr, the intermetallic Zr₃Fe with less than 0.2 at.% Nb in solution, two new ternary intermetallic compounds (Zr+Nb)₂Fe `λ<sub>1</sub>' with a cubic Ti<sub>2</sub>Ni-type structure in the composition range (2.4-13) at.% Nb and (31-33) at.% Fe, and (Fe+Nb)<sub>2</sub>Zr `λ₂' indexed as hexagonal Laves phase MgZn₂ type (C14) with a wide range of compositions close to (35-37) at.% Zr, (12-31) at.% Nb and (32-53) at.% Fe.     

Irradiated Behavior at High Burnup for HiFi Alloy

Irradiation tests of a BWR advanced Zr alloy (HiFi alloy) and Zircaloy-2 (Zry-2) were carried out in a Japanese commercial reactor and the irradiation performances of the materials were investigated. HiFi alloy and Zry-2 showed excellent resistance to corrosion up to 70 GWd/t, and furthermore, HiFi kept lower hydrogen pickup compared with Zry-2. TEM observation showed that the Fe/(Fe+Cr) ratio of Zr(Fe,Cr)2 type second phase particles (SPPs) for HiFi alloy and Zry-2 tended to decrease as fast neutron fluence increased and to saturate at high fluence. Zr-Fe-Cr SPPs did not completely disappear even for 6 cycles for the irradiated HiFi alloy and Zry-2. In order to clarify the mechanism of hydrogen absorption, an electrochemical technique was used for the oxide film of both materials as part of the out-of-pile test. The relation between the oxide surface potential and the hydrogen pickup fraction was estimated suggesting that the potential difference over the oxide film suppressed hydrogen (proton) diffusion in the oxide film.     

Zr-Fe-Nb合金中Zr(Nb,Fe)2相在400 ℃/10.3 MPa过热蒸汽中的腐蚀行为

Zr-1.0Fe-1.0Nb合金经β相油淬、冷轧变形及580 ℃/5 h退火处理,在静态高压釜中进行400 ℃/10.3 MPa过热蒸汽腐蚀试验,利用带EDS的SEM和HRTEM对合金基体以及腐蚀生成的氧化膜显微组织进行分析。结果表明：合金中主要存在正交的Zr 3Fe和密排六方的Zr(Nb,Fe)₂第二相。Zr(Nb,Fe)₂相在氧化过程中先转变成非晶组织,非晶进一步氧化转化为m-Nb₂O₅和m-Fe₂O₃相纳米晶态氧化物,最后扩散流失到腐蚀介质中;Zr(Nb,Fe)₂相氧化后的Fe、Nb元素发生扩散流失,且Nb的流失速度大于Fe,合金元素的扩散流失在氧化膜中留下大量缺陷,促进氧化膜由柱状晶向等轴晶形态演化而不利于合金的耐腐蚀。     

Evolution of microstructure and second-phase particles in Zr–Sn–Nb–Fe alloy tube during Pilger processing

Evolution of microstructure and second-phase particles (SPPs) in Zr–Sn–Nb–Fe alloy tube were investigated during Pilger process using electron backscatter diffraction, secondary electron and transmission electron microscopy imaging techniques. Results show that the Pilger rolled tubes present heterogeneous structures with the C axes of less deformed grains mostly concentrated in the axial direction. During the Pilger rolling, the increase of deformation caused weakening of linear distribution of second-phase particles. The mean diameters of the precipitates are in the range of 70–100 nm in all specimens, and the growth mechanism of SPPs follows second-order kinetics. The grain growth is controlled by Zener pinning in the Pilger rolling–annealing specimens. Clusters containing the Zr(Nb,Fe)₂ and β_Nb precipitates formed in the Zr–1.0Sn–1.0Nb–0.12Fe alloy. Most of the particles located in grain boundaries are the Zr(Nb,Fe)₂ Laves phase with hexagonal structure, and stacking faults have been found in the Zr(Nb,Fe)₂ precipitates. The types, morphology and distribution of precipitates depend on the constituent and structural fluctuations of the nucleation area.     

Effect of Heat Treatment in α+β Phase Field on Microstructure and Corrosion Property of Zr-Sn-Nb Alloy

Uniform corrosion tests were carried out with the specimens prepared by different heat treatments at the temperature in α+β phase field. The surface microstructure of specimens was observed by scanning electron microscope, the corrosion behavior was analyzed by autoclaves, and the oxide layer on the surface after the corrosion test was analyzed by focused ion beam (FIB) and atomic force microscope (AFM). The results show that after the heat treatment in α+β phase field, lamellar β-Zr phase appeares in the Zr matrix, and after the subsequent α phase final heat treatment, the β-Zr phase will be decomposed to α-Zr and discontinuous second phase particles. For the specimens heat treated in α+β phase field, after the α phase final heat treatment, the corrosion resistance under 360 ℃/18.6 MPa pure water condition is better than that of specimens without final heat treatment. The oxide film formed on the β-Zr protrudes on the oxide surface, on the contrary, after α phase final heat treatment, β-Zr decomposes, and the oxide layer is sunken in this area.     

α+β两相区热处理对Zr-Sn-Nb合金微观组织和腐蚀性能的影响

对Zr-Sn-Nb合金在α+β两相区温度下不同工艺热处理后所得样品,在360 ℃/18.6 MPa纯水环境中进行均匀腐蚀试验,并采用扫描电子显微镜（SEM）观察样品微观形貌、聚焦离子束（FIB）和原子力显微镜（AFM）分析腐蚀后样品表面氧化膜。结果表明,Zr-Sn-Nb合金在α+β两相区温度下热处理时,锆合金中会形成条带状β-Zr第二相,再经过α相区温度最终退火后,β-Zr区域会分解为α-Zr和第二相粒子;经α相区最终退火的样品,在360 ℃/18.6 MPa纯水中的耐腐蚀性能优于未经最终退火的样品;未退火样品中条带状β-Zr第二相区域的氧化膜较α-Zr基体的氧化膜厚,而经过α相区温度退火后β-Zr发生分解,该区域的腐蚀氧化膜出现凹陷。     

Corrosion behavior of Fe-Ni-Cr alloys in the molten salt of LiCl-Li2O at high temperature

At Korea Atomic Energy Research Institute (KAERI), we investigated the corrosion behavior of a series of Fe-Cr-Ni alloys with different chromium contents in molten LiCl and molten LiCl-25wt%Li₂O mixture at temperatures ranging from 923 to 1123 K. In molten LiCl, dense protective scale of LiCrO₂ grows outwardly while corrosion is accelerated by addition of Li₂O to LiCl. The basic fluxing of Cr₂O₃ by Li₂O would be the cause of accelerated corrosion. Because of low oxygen solubility and very high Li₂O activity in the molten LiCl-Li₂O mixture, Cr is preferentially corroded while Ni remains stable and thus, corrosion rate of the alloys in molten LiCl-Li₂O mixture increases with an increase in Cr content.     

Contribution to the study of the pseudobinary Zr1Nb–Oxygen phase diagram by local oxygen measurements of Zr1Nb fuel cladding after high temperature oxidation

This work is concerned with measurement of oxygen concentrations and construction of the pseudobinary Zr1Nb–O phase diagram, acceptable for diffusion models predicting the oxidation behavior of Zr1Nb fuel cladding during thermal transients such as LOCA. Oxygen concentrations were measured in existing phases in the wall of Zr1Nb nuclear fuel cladding tubes after the high-temperature oxidation. The oxygen concentrations at the α/α + β phase boundary in the α-Zr(O) layer have been determined using WDS method. Oxygen concentrations in the prior β-Zr were measured using two experimental methods (SIMS and TEA). Consequently, the ceiling of the oxygen concentration in β-Zr has been assessed based on the results of SIMS, TEA, and microhardness measurements. Eventually, the experimental results were compared to the pseudobinary Zr1Nb–O phase diagram, calculated using CALPHAD software, with satisfactory agreement. The effect of hydrogen was also examined.     

Effects of hydrogen content and temperature on fracture toughness of Zircaloy-4

The influence of hydrogen content and temperature on the fracture toughness of a Zircaloy-4 commercial alloy was studied in this work. Toughness was measured on CT specimens obtained from a rolled material. The analysis was performed in terms of J-integral resistance curves. The specimens were fatigue pre-cracked and hydrogen charged before testing them at different temperatures in the range of 293–473 K. A negative influence of the H content on material toughness was important even at very small concentrations, being partially restored when the test temperature increased. Except for some specimens with high H concentration tested at room temperature, the macroscopic fracture behaviour was ductile. The role of Zr-hydrides and Zr(Fe,Cr)₂ precipitates in the crack growth and the dependence with hydrogen content were analysed by observation of the fracture surfaces and determination of the Zr(Fe,Cr)₂ precipitates density on them.     

Irradiation Effects on Corrosion Resistance and Microstructure of Zircaloy-4

In order to investigate irradiation effects on nodular corrosion resistance of Zircaloy-4, an out-of-pile corrosion test was conducted using Zircaloy-4 specimens cut from the channel box of a fuel assembly irradiated in the BWR (Monticello reactor) up to the neutron fluence of 1.53×10²⁶ n/m² (E>1MeV). The corrosion test was carried out in high pressure steam of 10.3 MPa at 783 K for 24 h. No nodules appeared on the specimens cut from welded areas of the channel box and nodular corrosion resistance tended to be better with increasing neutron fluence. Microstructural evolution in the form of irradiation-induced release of Fe atoms from Zr(Fe, Cr)2 type precipitates was detected by an analytical electron microscope. It was found that the higher the concentration of dissolved Fe and Cr in the grains of Zircaloy-4, the better the nodular corrosion resistance.     

Grain boundary diffusion and segregation of Cr in α-Zr

⁵¹Cr diffusion along grain boundaries in polycrystalline α-Zr was measured by means of the radiotracer technique in the temperature range 449-680 K. The use of Harrison´s C and B kinetics provided direct data about grain boundary diffusivity (D_gb) and the apparent grain boundary diffusivity (P_gb) in the temperature range of power reactors service. The grain boundaries segregation factor s of Cr in α-Zr was determined at the limit of very dilute solute concentration.     

Corrosion behaviour of new Zr alloys

Corrosion studies have indicated that the most promising replacements for Zicaloy-2 are ZrCrFe, ZrVFe and probably ZrNbTa, provided they are in their optimized condition. These alloys are conventionally manufactured alloys. An internally oxidized ZrMgO alloy is even superior, from the corrosion and hydrogen uptake points of view, to the above-mentioned alloys. This alloy is of particular interest because the addition of MgO leads to no neutron penalty and the dispersion-strengthening entails the possibility of tailoring an alloy with the desired mechanical properties.     

Effect of β phase, precipitate and Nb-concentration in matrix on corrosion and oxide characteristics of Zr-xNb alloys

The corrosion test and oxide characterization were performed on the specimens having different Nb-content in the range of 0-5 wt%. The specimens were heat-treated at 570 °C for 500 h to get the α+β_Nb phase and at 640 °C for 10 h to get the α+β_Zr phase after β-quenching. The corrosion tests were carried out at 360 °C. In the low Nb-contents of 0.1-0.2 wt% where Nb was soluble in the matrix without the formation of Nb-containing precipitates or β phase, the samples showed the excellent corrosion resistance and their corrosion resistance was not affected by heat-treatment. The corrosion resistance was improved by the stabilization of tetragonal ZrO₂ and columnar oxide structure when all added Nb was soluble in the matrix to equilibrium concentration. In the high Nb-contents of 1.0-5.0 wt%, the corrosion rate was very sensitive to the annealing condition. The transformation of oxide crystal structure from tetragonal ZrO₂ to monoclinic ZrO₂ and oxide microstructure from columnar to equiaxed structure was accelerated in the samples having β_Zr phase, while retarded in the sample having β_Nb phase. This means that the formation of β_Nb phase resulted in the reduction of Nb concentration in the α matrix, thus the corrosion resistance was enhanced with the formation of β_Nb phase. From the corrosion test and oxide characterization, it is suggested that the equilibrium concentration of Nb in the α matrix would be a more dominant factor to enhance the corrosion resistance than the Nb-containing precipitates, supersaturated Nb, and β phase (β_Nb or β_Zr).     

A TEM study of the C15 type Zr(CrFe)2 Laves phase in Zircaloy-4

The intermetallic precipitates in Zircaloy-4 have been identified as the C15 type Zr(CrFe)₂ Laves phase using high order Laue zones and series diffraction patterns from the transmission electron microscope. A model for the transformation from the α-Zr matrix to the Zr(CrFe)₂ Laves phase has been constructed using the data on orientation relationships obtained from TEM diffraction patterns. A defect structure of R-type stacking variety has been found in the Zr(CrFe)₂ particles.     

低锡Zr—4包壳管电子束焊接时发生的合金元素蒸发现象

采用电子探针的波谱分析方法,对国产低锡Ｚｒ－４包壳管的环焊缝试样进行表面成份分析。分析结果表明,从焊缝的外边到内边缘,Ｓｎ,Ｃｒ,Ｆｅ元素的化学成份在统计上呈增大趋势,腐蚀后出现了白色产物的试样表层,其Ｓｎ,Ｃｒ,Ｆｅ元素含量相当程度地降低。这一事实表明,国产低锡Ｚｒ－４包壳管采用电子束焊接时,在一定的焊接规范环焊缝的合金元素存在严重蒸发现象,特别是合金中锡元素的蒸发使其锡元素含量低于０．５％,导     

Zr-Sn-Nb-Fe-V合金包壳管加工过程中第二相的演变

采用扫描电子显微镜（SEM）和透射电子显微镜（TEM）研究了Zr-0.2Sn-1.3Nb-0.2Fe-0.05V合金经热挤压、冷轧、中间退火包壳管坯以及经终轧及最终退火后成品管材第二相特征。结果表明,热挤压产生的β-Zr及第二相沿管坯轴向呈流线状分布,随着冷轧和退火的进行,亚稳相β-Zr发生分解,第二相逐渐均匀化,最终呈细小、均匀、弥散分布。合金成品管材第二相主要为BCC结构的β-Nb,含有少量FCC结构的Zr(NbFeV)₂。加工过程中析出相的平均直径变化不大,均小于100 nm。合金包壳管第二相尺寸分布与热处理过程中含Nb第二相溶解析出直接相关。     

Corrosion characteristics of reduced activation ferritic steel, JLF-1 (8.92Cr–2W) in molten salts Flibe and Flinak

Static corrosion tests were performed in molten salts, LiF–BeF₂ (Flibe) and LiF–NaF–KF (Flinak), at 500 °C and 600 °C for 1000 h. The purpose is to investigate the corrosion characteristics of reduced activation ferritic steels, JLF-1 (8.92Cr–2W) in the fluids. The concentration of hydrogen fluoride (HF) in the fluids was measured by slurry pH titration method before and after the exposure. The HF concentration determined the fluoridation potential. The corrosion was mainly caused by dissolution of Fe and Cr into the fluids due to fluoridation and/or electrochemical corrosion. Carbon on the surface might be dissolved into the fluids due to the corrosion, and this resulted to the decrease of carbide on the surface. The corrosion depth of the JLF-1 specimen, which was obtained from the weight losses, was 0.637 μm in Flibe at 600 °C and 6.73 μm in Flinak at 600 °C.     

Effects of ECC Water Injection Rate on Reflood Phase during LOCA

Some metal iodides such as of Fe, Al, Zr and Te are known to cause stress corrosion cracking (SCC) of Zircaloy just as iodine itself does. Therefore 15 metal iodides were selected as corrodants, and SCC tests were carried out using the internal gas pressurization method.

The results showed that: (1) only those metal iodides which react thermodynamically with Zr to produce ZrI₄ cause SCC of Zircaloy-2; (2) when SCC occurs, the reaction rate between the iodide and Zr seems to be a main factor in determining the SCC susceptibility; (3) gaseous ZrI₄ is the most corrosive agent; and (4) some species of metal iodides, such as PbI, cause SCC of Zircaloy-2 more easily than I₂ vapor.

Scanning electron microscope (SEM) examination and electron probe microanalysis (EPMA) on the fracture surface of failed specimens revealed that ZrI₄, formed as the reaction product between the metal iodides and Zr, might induce SCC of Zircaloy-2 rather than the iodides themselves.