The effect of grain boundary misorientation on the intergranular M23C6 carbide precipitation in thermally treated Alloy 690

The precipitation characteristics of chromium carbides on various types of grain boundaries in Alloy 690 thermally treated at 720 °C for 10 h were studied through transmission electron microscopy. Precipitation of the intergranular chromium carbides, identified as Cr-rich M₂₃C₆, was retarded on the low angle grain boundaries, compared to that on the random high angle grain boundaries on which coarse and discrete ones were found. They were rarely found on the coherent twin boundaries, however, needle-like ones were evolved on the incoherent twin and twin related Σ9 boundaries. Precipitation of the chromium carbides was also suppressed on the nearly exact coincidence site lattice boundaries such as Σ11 and Σ15, for which the Brandon criterion was fulfilled. The results of the intergranular M₂₃C₆ carbide precipitation were explained in terms of the influence of the grain boundary energy.     

Development of a single loop EPR test method and its relation to grain boundary microchemistry for alloy 600

A single loop electrochemical potentiokinetic reactivation test method has been developed for alloy 600 that produces good passivation on all the surfaces, good etching during the reactivation scan and no appreciable pitting. It is able to quantify and discriminate between samples with a wide range of degree of sensitization. The Pa value correlates well with the minimum level of chromium in the depletion regions at the grain boundaries. It has been shown that the width of the attacked regions is much larger than the width of chromium depletion regions and it does not show any direct correlation with either depth or width or with a volume parameter of chromium depletion regions. It has been shown that the chromium carbides are not attacked during the test and that the intragranular regions attacked during the test are the sites of chromium carbides in the grain matrix. A modified Pa parameter is shown to be sensitive down to 7.5 wt% chromium in the depletion regions and indicates that the intragranular carbides have shallower depletion profiles than those at grain boundaries. Comparison of the results of the single loop and the double loop tests showed a good correlation.     

Tracer diffusion of Mn in alloy D9 in presence of sodium

The diffusivity of manganese in vacuum annealed and cold worked alloy D9 in presence of sodium was measured by the standard tracer technique. The lattice diffusion coefficient of manganese in vacuum annealed alloy D9 specimens in the temperature range 773-873 K is given by the expression and that in cold worked alloy D9 specimens is given by where R is in J K⁻¹ mol⁻¹. The activation energy for diffusion in cold worked specimens is less than that in vacuum annealed specimens. The activation energy for diffusion of manganese in presence of sodium is almost four times less than that in various austenitic stainless steels reported in the literature.     

Embrittlement susceptibility induced by impurities segregation to grain boundaries in martensitic steels candidates to be used in ADS

Grain boundary microchemical characterization, by Auger electron spectroscopy, has been performed in the martensitic steel EM-10 doped with relevant spallation elements that are expected to be produced at the spallation target window in future Accelerator Driven Systems (ADS). A heat treatment of step-cooling was performed in all doped materials to accelerate impurity segregation. The results indicate that step-cooling promotes chromium and molybdenum enrichment at the grain boundaries in the four materials studied. Step-cooling promotes phosphorus segregation to grain boundaries in the reference material, in the material doped with titanium, and in the material doped with titanium, phosphorus and sulphur. Step-cooling also promotes titanium enrichment in the materials doped with this element. A relation among chromium, molybdenum and phosphorus has been observed in the alloy doped with titanium, phosphorus and sulphur suggesting co-segregation of these elements to grain boundaries or segregation of phosphorus at the interface of the matrix and the carbides rich in chromium and molybdenum.     

Pitting corrosion of the laser surface melted Alloy 600

The effect of laser surface melting (LSM) on the resistance to pitting corrosion of Ni-base Alloy 600 was investigated by a potentiodynamic polarization test in 1 M NaCl solutions at pH values of 4 and 10 at temperatures of 30, 60 and 90 °C. The pitting potentials of Alloy 600 were markedly increased by the LSM process, when compared with those of the non-laser treated Alloy 600. From the microscopic examination after the corrosion test, it was found that the pitting was initiated at the junction between a TiN inclusion and the matrix, possibly at the site of a sulfide physically associated with the TiN inclusion. The homogeneous micro-structure associated with the reduction of the inclusion size during the LSM process could be attributed to the improvement of the pitting corrosion properties in the LSM Alloy 600.     

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.     

Corrosion behavior of Inconel 690 and 693 in an iron phosphate melt

The corrosion resistance of Inconel 690 and 693 coupons submerged in an iron phosphate melt has been investigated. After 155 days in an iron phosphate melt at 1050 °C, which contained 30 wt% of a simulated low activity waste (LAW at Hanford), the weight loss of Inconel 690 and 693 was 14% and 8%, respectively. The overall corrosion rate, calculated from the initial and final dimensions of each coupon, was 1.3 and 0.7 μm/day for the Inconel 690 and 693, respectively. Scanning electron microscopy and X-ray diffraction of the submerged Inconel coupons after 155 days in the iron phosphate melt showed that an altered surface layer had formed which was depleted in nickel and consisted of a (Fe, Cr)₂O₃ solid solution. This altered layer appears to be chemically protective as indicated by the gradual reduction in weight loss which occurred with time in the iron phosphate melt. Inconel 693 appears to be a better candidate to use as an electrode in iron phosphate melts since its corrosion rate and weight loss was only about one half that of Inconel 690.     

Solid state synthesis of Mg-Ni ferrite and characterization by XRD and XPS

Single-phase magnesium-nickel ferrites with varying amounts of nickel and magnesium were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. A plot of lattice parameter versus composition of the ferrites (Mg_xNi_(1−x)Fe₂O₄, x?1) showed an abrupt deviation of lattice parameter linearity near MgFeO₄. The deviation was explained in terms of the distribution of Mg²⁺ in the octahedral and tetrahedral sites of the oxygen lattice. In XPS spectra, a broadening of the Mg 1s peak in Ni rich Mg-Ni ferrites from that observed in pure MgFe₂O₄, was explained by changes in the distribution of Mg²⁺ ion in tetrahedral and octahedral sites. A depth distribution of Mg in Ni_0.5Mg_0.5Fe₂O₄ showed an enrichment of Mg on surface.     

Spectroscopic and microscopic study of the corrosion of iron–silicon steel by lead–bismuth eutectic (LBE) at elevated temperatures

The performance of iron–silica alloys with different silicon composition was evaluated after exposure to an isothermal bath of lead–bismuth eutectic (LBE). Four alloys were evaluated: pure iron, Fe–1.24%Si, Fe–2.55%Si and Fe–3.82%Si. The samples were exposed to LBE in a dynamic corrosion cell for periods from 700 to 1000 h at a temperature of 550 °C. After exposure, the thickness and composition of the oxide layer were examined using optical microscopy, scanning electron microscopy (SEM) and X-ray photoelectron spectrometry (XPS), including sputter depth profiling. Particular attention was paid to the role, spatial distribution, and chemical speciation of silicon. Low-binding-energy silicon (probably silicates or ) was found in the oxide; while elemental silicon (Si) was found in the metal as expected, and silica (SiO₂) was found at the bottom of the oxide layer, consistent with the formation of a layer between the oxide and the metal. Alloys with low concentrations of Si contained only silicate in the oxide. Alloys with higher concentrations of Si contained a layer of silica at the boundary between the oxide and the bulk metal. All of the alloys examined showed signs of oxide failure. This study has implications for the role of silicon in the stability of the oxide layer in the corrosion of steel by LBE.     

Recrystallisation of amorphous natural brannerite through annealing: The effect of radiation damage on the chemical durability of brannerite

An amorphous natural brannerite sample was chosen to study the annealing of the radiation damage through thermal recrystallisation, and subsequently to evaluate the effect of radiation damage on its aqueous durability. Microstructural characterisation of the natural brannerite revealed minor alteration along the rim of the crystal and within cracks. The formation of UO₂ particles and soluble Pb–Ca-rich aluminosilicate glass is responsible for the higher U and Pb releases from the recrystallised brannerite. In general, natural brannerite has been shown to be resistant to dissolution over geological time, therefore minor brannerite inclusions in ceramic formulations for immobilisation of actinide-rich radioactive wastes should not have a detrimental effect on the long-term chemical durability of the wasteforms.     

Studies on weldability of Ti-5Ta-1.8Nb alloy

The welding, qualification and characterization of welds of Ti-5Ta-1.8Nb alloy, which is being developed for high corrosion resistant performance, are reported. Based on the studies performed as per the ASME Section IX standards, welding procedure specification and procedure qualification record have been formulated. The heterogeneous microstructures of the weldment are rationalized, based on phase transformation in the alloy system and differences in the thermal cycles of various microscopic regions.     

Characterization of phases in ‘crud’ from boiling-water reactors by transmission electron microscopy

This paper reports phases identified in samples of crud (activated corrosion products) from two commercial boiling-water reactors using transmission and analytical electron microscopy and selected-area electron diffraction. Franklinite (ZnFe₂O₄) was observed in both samples. Hematite (α-Fe₂O₃), crystalline silica (SiO₂), a fine-grained mixture of iron oxides probably including magnetite (Fe₃O₄), hematite (α-Fe₂O₃), and goethite (α-FeOOH), and an unidentified high-Ba, high-S phase were observed in one of the samples. Willemite (Zn₂SiO₄), amorphous silica, and an unidentified iron-chromium phase were observed in the other. Chloride-bearing phases were found in both samples, and are assumed to represent sample contaminants. Because of the small sample volumes and numbers of particles studied and the possibility of contamination, it is not clear whether the differences between the phases observed in the two crud samples represent actual differences in the assemblages formed in the reactors.     

Influence of Nb concentration in the α-matrix on the corrosion behavior of Zr-xNb binary alloys

The influence of the Nb concentration in the α-matrix on the corrosion behavior of Zr-xNb (x=0-0.6 wt%) binary alloys was evaluated using a static autoclave in the temperature range from 300 to 500 °C. Corrosion tests and precipitate analysis of Zr-xNb binary alloys showed that corrosion resistance increased with the increase of the Nb concentration in the α-matrix, and the best corrosion resistance was obtained when the Nb concentration was nearly at its equilibrium solubility limit at all test temperatures. The alloys containing a higher Nb concentration than their equilibrium solubility also showed good corrosion resistance, which could be attributed mainly to the formation of Nb-precipitates, resulting in an equilibrium Nb concentration in the α-matrix. These results imply that the corrosion resistance of Nb-containing Zr-alloys can be controlled by the Nb concentration in the α-matrix rather than the Nb-precipitates.     

The influence of proton irradiation on the corrosion of HT-9 during immersion in lead bismuth eutectic

The impedance properties of the oxide on the martensitic-ferritic steel HT-9 were characterized during proton irradiation at the LANSCE WNR facility. Prior to the irradiation experiment, samples were pre-oxidized in moist air resulting in an oxide scale that was on the order of 3 μm thick. Samples were then irradiated during immersion in 473 K lead-bismuth eutectic at a proton current of approximately 63 nA. To assess corrosion rate in real-time, a sinusoidal voltage perturbation was applied across the oxide surface as a function of frequency and the corresponding current response was measured. This method yielded values of oxide impedance which were used in conjunction with Wagner’s oxidation theory to calculate corrosion rate. In general, proton irradiation was associated with an increase in corrosion rate.     

Vitrification of high chrome oxide nuclear waste in iron phosphate glasses

A simulated high level waste (HLW) containing 4 mass% chrome oxide, whose overall composition is representative of the high chrome oxide wastes at Hanford WA USA, was easily vitrified in a phosphate glass at temperatures ranging from 1150 °C, for waste loadings of 55 mass%, to 1250 °C for waste loadings of 75 mass%. Even at these high waste loadings, these wasteforms had an excellent chemical durability. The best chemical durability was achieved when the O/(Si + P) atomic ratio was between 3.5 and 3.8. These wasteforms were also resistant to crystallization although trace amounts of crystalline Cr₂O₃ were present in wasteforms containing more than 70 mass% HLW. It is concluded that up to 45 mass% of the total HLW at Hanford, especially that containing as high as 4.5 mass% chrome oxide, could be directly vitrified into an iron phosphate glass, that meets all of the current chemical durability requirements by simply adding 25-35 mass% P₂O₅ to the waste and melting the mixture at 1150-1250 °C for a few (<6) hours.     

Influence of ageing heat treatment on alloy A-286 microstructure and stress corrosion cracking behaviour in PWR primary water

The influence of ageing heat treatment on alloy A-286 microstructure and stress corrosion cracking behaviour in simulated Pressurized Water Reactor (PWR) primary water has been investigated. A-286 microstructure was characterized by transmission electron microscopy for ageing heat treatments at 670 °C and 720 °C for durations ranging from 5 h to 100 h. Spherical γ′ phase with mean diameters ranging from 4.6 to 9.6 nm and densities ranging from 8.5 × 10²² m⁻³ to 2 × 10²³ m⁻³ were measured. Results suggest that both the γ′ phase mean diameter and density quickly saturate with time for ageing heat treatment at 720 °C while the γ′ mean diameter increases significantly up to 100 h for ageing heat treatment at 670 °C. Grain boundary η phase precipitates were systematically observed for ageing heat treatment at 720 °C even for short ageing periods. In contrast, no grain boundary η phase precipitates were observed for ageing heat treatments at 670 °C except after 100 h. Hardening by γ′ precipitation was well described by the dispersed barrier hardening model with a γ′ barrier strength of 0.23. Stress corrosion cracking behaviour of A-286 was investigated by means of constant elongation rate tensile tests at 1.5 × 10⁻⁷ s⁻¹ in simulated PWR primary water at 320 °C and 360 °C. In all cases, initiation was transgranular while propagation was intergranular. Grain boundary η phase precipitates were found to have no significant effect on stress corrosion cracking. In contrast, yield strength and to a lesser extent temperature were found to have significant influences on A-286 susceptibility to stress corrosion cracking.     

Microstructural investigation of the stability under irradiation of oxide dispersion strengthened ferritic steels

Some fuel pin cladding made from a ferritic steel reinforced by titanium and yttrium oxides were irradiated in the French experimental reactor Phénix. Microstructural examination of this alloy indicates that oxides undergo dissolution under irradiation. This irradiation shows the influence of dose and, in a smaller part, of temperature. In order to better understand the mechanisms of dissolution, three ferritic steels reinforced by Y₂O₃ or MgO were irradiated with different charged particles. Inelastic interactions induced by 1 MeV He ion irradiation do not lead to any modification, neither in their chemical composition, nor in their spatial and size distribution. In contrast, isolated Frenkel pairs created by electron irradiation lead to significant oxide dissolution with a radius decrease proportional to the dose. Moreover, the comparison between irradiation with ions (displacements cascades) and electrons (Frenkel pairs only) shows the importance of free point defects in the dissolution phenomena.     

Contribution to the understanding of the ZrNb(l%)O(0.13%) oxidation mechanism at 500 °C in dry air

The oxidation of ZrNb(l%)O(0.13%) at 500 °C in dry air was investigated in situ by thermogravimetric analyses and electrochemical impedance spectroscopy. Sheets of the alloy were coated with different noble metals (Pt, Au, Ag) as electrode material. After an initial sub-parabolic rate law, the kinetics of ZrNb(l%)O(0.13%) oxidation are characterized by a transition to another decreasing rate law for different times and thicknesses. Noble metals were observed to clearly modify the oxidation rate, even when a pre-oxidized zirconia film was formed before the deposit and the increase in the oxidation rate was always monitored for thick oxides (30 μm). The kinetic transition is hypothesized to be associated with the microstructural degradation of the oxide film. Localized oxidation rate increases were revealed by scanning electron microscopy at the tip of radial cracks distributed on more than 2% of the total area of the sample. Catalytic effects observed on the oxidation rate after the noble metal deposition suggest that the mechanism controlling the oxidation rate is not a solely one of oxygen diffusion through the oxide layer. The reaction of oxygen reduction at the oxide/metal/gas interface partially controls the oxidation kinetics of ZrNb(l%)O(0.13%). Complex electrical signatures monitored during the oxide growth corroborate this assumption and hence indicate that oxygen reduction is still partially controlling the oxidation rate when noble metal are present on ZrNb(l%)O(0.13%) surface. Finally, a mixed process of interfacial-diffusion mechanism is proposed to be the rate determining step for ZrNb(l%)O(0.13%) oxidation in this environment.     

Influence of irradiation temperature and dose gradients on the microstructural evolution in neutron-irradiated 316SS

A cold worked 316SS baffle bolt was extracted from the Tihange pressurized water reactor and sectioned at three different positions. The temperature and dose at the 1-mm bolt head position were 593 K and 19.5 dpa respectively, whereas at two shank positions the temperature and dose was 616 K and 12.2 dpa at the 25-mm position and 606 K and 7.5 dpa at the 55-mm position. Microstructural characterization revealed that small faulted dislocation loops and cavities were visible at each position, but the cavities were most prominent at the two shank positions. Measurable swelling exists in the shank portions of this particular bolt, and accompanying this swelling is the retention of very high levels of hydrogen absorbed from the environment. The observation of cavities in the CW 316SS at temperatures and doses relevant to LWR conditions has important implications for pressurized water reactors since SA 304SS plates surround the bolts, a steel that usually swells earlier due to its lower incubation period for swelling.     

Studies on the corrosion behavior of cerium-implanted zirconium

In order to study the influence of cerium ion implantation on the aqueous corrosion behavior of zirconium, specimens were implanted with cerium ions with a fluence ranging from 1 × 10²⁰ to 1 × 10²¹ ions/m² at about 150 °C, using a MEVVA source at an extracted voltage of 40 kV. The valence and element penetration distribution of the surface layer were analyzed by X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES) respectively. The potentiodynamic polarization technique was employed to investigate the aqueous corrosion resistance of zirconium in a 1N H₂SO₄ solution. It was found that there was a remarkable improvement in the aqueous corrosion behavior of zirconium implanted with cerium ions compared with that of the as-received zirconium. The corrosion resistance improvement of the cerium-implanted zirconium is probably due to the addition of cerium oxide dispersoid into the zirconium matrix and oxidization protection.