On the Use of NaOH Solution to Simulate the Crevice Conditions of a Nuclear Steam Generator.

The corrosion behavior and integrity of steam generator (SG) tube materials have frequently been tested in solutions containing sodium hydroxide (NaOH), assuming that NaOH is a typical contaminant concentrated in the crevices of SGs in a pressurized water reactor. The purpose of this study was to investigate the adequacy of using concentrated NaOH solutions to simulate the crevice environments of SGs. The dissolution behavior of magnetite deposit flakes formed in an operating SG was tested in a 0.4 wt.% NaOH solution at 300 °C, and the thermodynamic stability of magnetite was investigated using the potential-pH diagram for an iron-water system. The magnetite deposits were rapidly dissolved in the test solution, which was supported by the fact that magnetite is thermodynamically unstable under the test condition to dissolve to dihypoferrite ions (HFeO2-). These results indicate that research data obtained from concentrated NaOH solutions are not appropriate to apply to the crevice environments of SGs.

Chemical Cleaning of Magnetite Deposits on the Flow Mini-Channels of a Printed Circuit Heat Exchanger in an EDTA-Based Solution.

The dissolution behavior of magnetite deposited on flow mini-channel surfaces within a printed circuit heat exchanger (PCHE) and the corrosion behavior of a STS 316L PCHE material were investigated in an ethylendiaminetetraacetic acid (EDTA)-based chemical cleaning solution at 93 °C. The fouling in the PCHE was simulated using a water-steam circulation loop system. Most of the magnetite deposits were rapidly dissolved in the early stage of the circulation chemical cleaning. An empirical equation for estimating the dissolution percentage was derived as a function of cleaning time. The PCHE material showed excellent corrosion resistance during the chemical cleaning tests. These results indicate the fouling layers in the PCHEs can be removed efficiently by the chemical cleaning process without concern about base metal corrosion.

Effect of Tensile Stress on the Oxide Properties of a Nickel-Based Alloy 600 in Simulated PWR Secondary Water.

The purpose of this work was to examine the effect of tensile stress on the oxide properties of a nickel-based Alloy 600 that was exposed to simulated nuclear steam generator water at 340 °C for 1000 h. The size of the outer oxide particles increased, and the chromium content of the inner oxides decreased under tensile stress. Electrochemical measurements revealed that the charge carrier density increased, and the charge transfer resistance and film resistance were reduced under the tensile stress condition. These changes in the oxide properties are attributed to the formation of short diffusion paths such as line and surface defects due to tensile deformation.

Effects of Zinc Addition on the Corrosion Behavior of Pre-Filmed Alloy 690 in Borated and Lithiated Water at 330 °C.

The purpose of this work is to quantify the effects of dissolved zinc cations on corrosion and release rates from a pre-filmed Alloy 690 steam generator tubing material that was subsequently exposed to water containing zinc. The corrosion tests were performed in circulating 2 ppm Li and 1000 ppm B water without and with 60 ppb zinc at 330 °C. Gravimetric analyses and oxide characterization revealed that the corrosion rates, release rates, and oxide thicknesses decreased by subsequent exposure of the pre-filmed Alloy 690 to zinc. These benefits are attributed to the formation of a chromium-rich inner oxide layer incorporating zinc.

Behavior of Zinc Incorporation into Fuel Deposits in Borated and Lithiated Water with Dissolved Zinc.

The objective of this study was to investigate the behavior of zinc incorporation into newly forming fuel deposits and pre-formed deposits in a simulated pressurized water reactor coolant including 1000 ppm of boron and 2 ppm of lithium at 328 °C. Zinc was incorporated into fuel deposits that were being newly nucleated and grown on nuclear fuel cladding tubes in a zinc-containing coolant. The zinc incorporation resulted in a decrease in the lattice constant of the deposits, which was attributed to the decrease in larger iron content and the corresponding incorporation of smaller zinc in the deposits. However, zinc incorporation was not found, even after the fuel deposits pre-formed before zinc addition were subsequently exposed to the 60 ppb of zinc coolant for 500 h.

Zeta Potentials of Magnetite Particles and Alloy 690 Surfaces in Alkaline Solutions.

Magnetite particles deposited on the secondary side of a steam generator (SG) can degrade the integrity and performance of pressurized water reactors. Therefore, it is necessary to produce the data of fundamental interfacial electrokinetic properties of magnetite particles and SG tube materials. This study investigated the zeta potentials of magnetite nanoparticles and Alloy 690 surfaces, which were dependent on the pH value, pH agent, and the presence of NaCl. The zeta potentials of the magnetite nanoparticles increased in the negative direction as the pH increased, regardless of the pH agent. At the same pH value, the absolute values of the zeta potentials with different pH agents were: ethanolamine < ammonia < morpholine. In the presence of NaCl, the zeta potentials of the particles further increased negatively. The meaning of the measured zeta potentials was discussed in terms of the dispersion stability and the agglomeration of the particles. Based on the relationship between the zeta potentials of the particles and Alloy 690 surfaces, the magnetite deposition on Alloy 690 was also discussed. Furthermore, the empirical formulas for the pH-dependent zeta potentials of magnetite particles in each alkaline solution were suggested.

Molar Ratio Effect of Sodium to Chloride Ions on the Electrochemical Corrosion of Alloy 600 and SA508 in HCl + NaOH Mixtures.

This study aims to investigate the molar ratio effect of sodium to chloride ions on the corrosion of an Alloy 600 steam generator tube and an SA508 tubesheet material. The corrosion behavior was evaluated in solutions with three different molar ratios of sodium to chloride ions using a potentiodynamic polarization method. The corrosion potentials and corrosion rates of both the two materials were significantly decreased as the molar ratio increased from 0.1 to 10. Therefore, it is recommended that the molar ratio control to a value of 1 is beneficial only when the crevice chemistry has a low molar ratio with an acidic pH. The corrosion potentials and corrosion rates were little affected by the total sodium and chloride ion concentrations. SA508 acted as an anode and its corrosion rate was accelerated by galvanic coupling with Alloy 600.

Stress Corrosion Cracking Behavior of Alloy 600 Coupled to Magnetite under High-Temperature Caustic Conditions.

This study aims to investigate and explain the magnetite-accelerated stress corrosion cracking phenomenon of Alloy 600 under caustic conditions, based on the electrochemical behavior. After the SCC test that lasted for 300 h, no cracks were observed in any of the magnetite-free specimens, whereas cracks with a depth of 150 to 280 µm were generated in all the magnetite-deposited specimens. Furthermore, the electrochemical behavior of magnetite and Alloy 600 demonstrated that Alloy 600 behaved as an anode in the coupling system with magnetite. In this coupling system, the electrochemical potential of Alloy 600 can be shifted into the range potentially susceptible to stress corrosion cracking.

Galvanic Corrosion of SA106 Gr.B Coupled with Magnetite in Alkaline Solution at Various Temperatures.

The effect of temperature on the galvanic corrosion behavior of SA106 Gr.B carbon-manganese steel was studied in an alkaline aqueous solution at various temperatures (30, 60, and 90 °C) via electrochemical corrosion tests. At all temperatures studied, carbon-manganese steel acted as the anode of the galvanic cell composed of carbon-manganese steel and magnetite because the corrosion potential of carbon-manganese steel was significantly lower than that of magnetite. The corrosion current density of carbon-manganese steel significantly increased due to the galvanic effect irrespective of temperature used in this study. With the increase in temperature, the extent of the galvanic effect on the corrosion current density of carbon-manganese steel and reductive dissolution of magnetite gradually increased. When the area ratio of magnetite to carbon-manganese steel increased, the corrosion rate of the carbon-manganese steel in contact with magnetite further increased.

Effects of Hydrogen Contents on Oxidation Behavior of Alloy 690TT and Associated Boron Accumulation within Oxides in High-Temperature Water.

The aim of this work is to characterize the oxide layer structure of Alloy 690TT in high-temperature water with different dissolved hydrogen (DH) contents by using an X-ray photoelectron spectroscopy. Under the low DH contents (0.4494-0.8988 mg/kg), the oxide layers were composed of an outermost layer of Ni(OH)2 and Cr(OH)3 enriched in Ni, an intermediate layer of hydroxides and oxides enriched in Cr, and an inner Cr2O3 layer. Outermost NiO coexists with small amount of Cr2O3 layer, while in the inner oxide only Cr2O3 remains. The oxide layers at medium and high DH contents (3.1458- 8.9880 mg/kg) consisted of an outermost layer of Ni(OH)2 and Cr(OH)3 enriched in Cr, an intermediate layer of metallic Ni, hydroxides and oxides enriched in Cr, and an inner Cr2O3 layer. In addition, boron compounds containing B3+ ions were accumulated in the thick and porous NiO layer formed at low DH contents, whereas the accumulation of boron compounds did not occur in the thin and dense polyhedral oxide layer formed at medium and high DH contents.

Simulating Porous Magnetite Layer Deposited on Alloy 690TT Steam Generator Tubes.

In nuclear power plants, the main corrosion product that is deposited on the outside of steam generator tubes is porous magnetite. The objective of this study was to simulate porous magnetite that is deposited on thermally treated (TT) Alloy 690 steam generator tubes. A magnetite layer was electrodeposited on an Alloy 690TT substrate in an Fe(III)-triethanolamine solution. After electrodeposition, the dense magnetite layer was immersed to simulate porous magnetite deposits in alkaline solution for 50 days at room temperature. The dense morphology of the magnetite layer was changed to a porous structure by reductive dissolution reaction. The simulated porous magnetite layer was compared with flakes of steam generator tubes, which were collected from the secondary water system of a real nuclear power plant during sludge lancing. Possible nuclear research applications using simulated porous magnetite specimens are also proposed.