Degradation of corrosion resistance of Zircaloy-4 in LiOH aqueous solution

To investigate the degradation of corrosion resistance of Zircaloy-4 in LiOH aqueous solution, SIMS (secondary ion mass spectrometry) analysis was performed to examine the profiles of Li+, K+, and OH- in oxide layers formed in the same concentration (0.1 mol/L) LiOH and KOH solutions. Even though the oxide layers have an equal thickness, the penetration depth of K+ is shallower than that of Li+, and the penetration depth of OH- corroded in KOH solution is also shallower than that corroded in LiOH solution. It shows that the diffusion of OH- into oxide layer is accompanied by the corresponding cation. The difference of degradation effect of LiOH and KOH solutions on the corrosion resistance of Zircaloy-4 was discussed.     

Detrimental role of LiOH on the oxide film formed on Zircaloy-4

To understand the degradation behavior of Zircaloy-4 corroded in LiOH aqueous solution, X-ray diffraction was performed to analyze the crystal structure of Zircaloy-4 oxide formed in three different media. Second ion mass spectrometry (SIMS) was utilized to measure the penetration of Li⁺ and OH⁻ into the oxide film when Zircaloy-4 is exposed in LiOH aqueous solution. It was found that the SIMS depth profile of OH⁻ in the oxide film is in accord with that of Li⁺, which indicates that there exists OH⁻ in the oxide film. Based on the results, it is put forward that OH⁻ diffuses faster than O⁻² in the oxide films, which can enhance the corrosion rate of Zircaloy-4 and the transformation from tetragonal zirconia (t-ZrO₂) to monoclinic zirconia (m-ZrO₂). OH⁻ plays a detrimental role on the oxide film formed on Zircaloy-4.     

Stress corrosion cracking of zirconium and Zircaloy-4 in halide aqueous solutions

Zirconium and Zircaloy-4 in 1 M NaCl, 1 M KBr and 1 M KI aqueous solutions were found to be susceptible to stress corrosion cracking (SCC) only at potentials above the pitting potential. In all the tested systems the following steps were found: first electrochemical breakdown of the passive film, followed by intergranular attack due to anodic dissolution assisted by stresses; and finally a fast transgranular propagation. This last step was identified as the “true” SCC process. The analysis of the possible mechanisms involved during this process led to the conclusion that the surface-mobility SCC mechanism can be used to explain the experimental results found in the present work.     

Plasma electrolytic oxidation and corrosion protection of Zircaloy-4

The compositions and morphologies of coatings formed by plasma electrolytic oxidation (PEO) on Zircaloy-4 in silicate electrolyte, using an AC current regime, have been determined for a range of formation times. The coatings consist of zirconia with incorporated silicon species, with the distributions of coating species related to the types of discharges. Potentiodynamic polarization in 6 M nitric acid at 100 °C indicated that the corrosion resistance is mainly provided by the thin barrier layer next to the substrate.     

LiOH水溶液加速Zr-4合金腐蚀的研究

将Zr-4合金样品分别放在盛有350℃,0．1mol／L的LiOH和KOH水溶液的高压釜中进行腐蚀,当2种样品的氧化膜厚度相同时,用二次离子质谱仪(SIMS)测量Li^ ,K^ 和OH^-在氧化膜剖面上的浓度分布,发现进入氧化膜的Li^ 比K^ 深而且记数强度高,同时在LiOH水溶液中腐蚀的样品,其氧化膜中OH^-的强度也比在KOH水溶液中腐蚀的样品高,这表明OH^-在氧化膜中的分布和扩散与其对应的阳离子有关。根据以上结果讨论了Zr-4合金在LiOH水溶液中耐腐蚀性能降低的原因。     

Analysis of microstructure and corrosion behavior of laser surface alloyed zircaloy-4 with niobium

The influence of laser surface alloying (LSA) with niobium (Nb) on the corrosion and mechanical properties of Zircaloy-4 was examined by potentiodynamic polarization testing in a chloride solution at 80°C and microhardness testing. The results are discussed with the structural and compositional variations in the LSA layer determined by X-ray diffraction (XRD), a scanning electron microscope (SEM) and a wavelength dispersive spectrometer (WDS). The LSA on Zircaloy-4 precoated with Nb produced a Nb-alloyed layer 200~300 μrn thick with 1.3~2.5 wt.% Nb, depending on the laser beam power. The alloyed layer was composed of a mixed structure of α-Zr and β-Zr phases with the (β-Zr phase increasing with the Nb content in the alloyed layer. The LSA with Nb increased the microhardness of Zircaloy-4, which was attributed primarily to the grain-size refinement of rapid cooling and, also, to the solid solution hardening with Nb. The resistance to the localized corrosion of Zircaloy-4 in a chloride solution significantly improved through LSA with Nb, which was attributed to the combined effects of the fine rapidly cooled microstructure and to the Nb alloying.     

Electrochemical and XPS studies and the potential scan rate dependent pitting corrosion behavior of Zircaloy-2 in 5% NaCl solution

Electrochemical studies of Zircaloy-2 in 5% NaCl solution were carried out using polarization and electrochemical impedance spectroscopy (EIS). Scan rate dependent pitting behavior of Zircaloy-2 was observed when polarization experiments were carried out at different scan rates (5 mV/min, 50 mV/min and 500 mV/min). Polarization resistance, double layer capacitance, and the thickness of passive film were calculated from the EIS study. The slope of the Bode plot in the capacitive region showed non-ideal behaviour, suggesting formation of pits. A distribution of chloride concentration was seen at the surface of the electrode when the test solution was sampled from different parts of the sample surface and analyzed for chloride. Inclusion of chloride ions in the passive film was observed from the XPS study and the chloride concentration increases with the higher anodic polarization. The outermost layer of the passive film was rich in hydroxide and oxy-hydroxide. A bi-layer passive film structure on the alloy surface is proposed.     

Fretting wear behavior of nitrogen implanted Zircaloy-4 alloy

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激光表面处理对Zr－4合金板材疖状腐蚀的影响

研究了几种激光表面处理工艺对不同状态的Ｚｒ－４合金板材泡疖腐蚀的影响。实验结果表明：激光表面处理可以显著提高Ｚｒ－４合金抗疖状腐蚀性能；激光表面处理前Ｚｒ－４合金板材的状态（消除应力退火态、再结晶退火态、冷加工态）对激光表面处理后板材的疖状腐蚀性能的影响不明显     

Zr-4合金氧化膜的显微组织研究

Zr-4合金样品在高压釜中经过360℃/18.6 MPa高温去离子水腐蚀395天后,用扫描电镜观察了氧化膜的断口形貌,用高分辨透射电镜观察了氧化膜不同深度处的显微组织和晶体结构,研究了氧化膜的显微组织在腐蚀过程中的演化过程。氧化膜的晶体结构非常复杂,在靠近金属基体处除了稳定的单斜(m)晶体结构外,还存在非晶、立方(c)和四方(t)等亚稳相,晶体中还生成了很多缺陷。m/t和m/c晶体之间存在共格关系,满足(001)m//(110)t,(010)m//(1-10)t;以及(001)m//(002)c,(010)m//(020)c的取向关系。氧化膜中的晶体缺陷在应力、温度和时间作用下会发生扩散,并在氧化锆晶界上凝聚生成孔隙,弱化了晶粒之间的结合力并引起显微组织的演化。在内应力的作用下,孔隙之间的扩展和连结发展成微裂纹,氧化膜变得比较疏松,导致了耐腐蚀性能的变化和腐蚀加速。讨论了各种影响显微组织演化因素之间的关系,氧化膜显微组织的演化过程是不可避免的,寻找并控制能够延缓显微组织演化过程的因素是提高锆合金耐腐蚀性能的有效途径。     

Laser pulsed welding in thin sheets of Zircaloy-4

A simulation technique for the welding process design to obtain the high reliability of nuclear fuel spacer grids is presented. A finite element model of pulsed laser welding for Zircaloy-4 plate is developed, which incorporates the phase transitions and the dynamic material properties with transient temperature. The effects of pulsed laser parameters on the pool shape and welding-induced distortion are analyzed by simulations and verified by experiments. The parametric study presents that the welding induced distortions are highly dependent on the geometry of the molten zone and the heat affected zone.     

Corrosion-erosion resistance of Zn-Al co-cementation coatings on carbon steels in aqueous media

A novel Zn-Al co-cementation coating was obtained by a pack cementation method,This coating possesses a two-layered structure,The outer layer is mainly composed of Fe2Al3 and FeAl intermetallics with a small amount of Zn,and the inner layer consists of Zn,Fe and a small amount of Al.The corrosion-erosion resistance of Zn-Al con-cementation coatings on carbon steel was studied by a rotary corrosion method in various NaCl and H2S containing solutions and relevant SiO2 containing media,The experimental results are compared with those of carbon steels and the sherardizing and aluminizing coating ,showing that the Zn-Al co-cementation coating have excellent corrosion-erosion resistance in various aqueous media.     

Intergranular to transgranular transition in the stress corrosion cracking of Zircaloy-4

Stress corrosion cracking susceptibility of Zircaloy-4 wires was previously studied in 1 M NaCl, 1 M KBr and 1 M KI aqueous solutions and in iodine alcoholic solutions. In all cases, intergranular attack preceded transgranular propagation. It is generally accepted that the intergranular-transgranular transition occurs when a critical value of the stress intensity factor is reached. In the present paper it was confirmed that the transition from intergranular corrosion to transgranular propagation in Zircaloy-4 wires occurs when a critical value of the stress intensity factor is reached. This critical stress intensity factor in wire samples is independent of the solution tested and close to 11 MPa m^−1/2. This value is in good agreement with those reported in the literature measured by different techniques and with different specimen geometries.     

Electrochemical oxidation of pyrrhotute in aqueous solution

The anodic surface oxidation of natural pyrrhotite in 0.3 mol/L KCI and HCI solution （pH 4.0） and 0.1 mol/L Na2B4O7 solution （pH 9.18） respectively was investigated by using cyclic voltammetry, Tafel plot, and chronoamperometry. In 0.3 mol/L KCl and HCl solution （pH 4.0）, at potential less than 0.5 V（vs SHE）, the production of anodic oxidation on pyrrhotite surface can not maintain a stable phase to form a passive film. In 0.1 mol/L Na2B4O7 solution （pH 9.18）, when the electrode potential increases to more than 0.5 V （vs SHE）, part of S is oxidized to sulfate, making the passive film somewhat porous, but elemental S and metal oxidates Fe（OH）3 still remain on the electrode surface, and the passive film can not be broken down totally. According to PARCalc Tafel analysis, the corresponding corrosion current density （J0） is 5.34 μA/cm^2 , which is also the exchange current density of the oxidation reaction on pyrrhotite electrode surface in 0. 1 mol/L Na2B4O7 solution （pH 9. 18）. The electrochemical dynamics equation of the oxidation was determined.     

碳含量及固溶温度对镍基合金复合板耐蚀性及冲击韧性的影响

采用控轧控冷(TMCP)工艺制备了N08825镍基合金/X70(碳含量为0.16％)复合板和N08825镍基合金/700L(碳含量为0.069％)复合板,并对复合板进行了900～1200℃的固溶处理,利用光学显微镜(OM)和扫描电镜(SEM)研究了不同温度固溶处理后复合板界面碳化物形貌和分布、耐蚀性和冲击韧性.结果 表...     

镍基惰性阳极的耐腐蚀性研究(上)

论述NiO-NiFe2O4基金属陶瓷惰性阳极在熔融电解质中的腐蚀情况,对该镍基惰性阳性的制备过程及抗腐蚀性能进行了深入研究。     

调整处理对17-4PH不锈钢耐海水腐蚀性能的影响

运用化学浸泡、极化曲线、循环极化曲线、电化学阻抗谱等方法研究了固溶后直接时效状态和调整＋时效状态的17—4PH不锈钢在人工海水中的耐蚀性能，并对显微组织作了观察和分析。结果表明，17—4PH不锈钢过调整处理后再进行时效处理，自腐蚀电位和点蚀电位升高而年腐蚀率下降，耐海水腐蚀性能全面优于直接时效态试样。其原因是17-4PH不锈钢经过调整处理后进行时效可避免贫铬区的形成，并使马氏体组织呈细小化特征，材料的组织均匀性提高。     

Initial atmospheric corrosion of zinc in presence of Na_2SO_4 and (NH_4)_2SO_4

1 Introduction In view of the widespread use of zinc, as metallic sheet or zinc coatings, it was desirable to study its corrosion behaviour in the wide variety of atmospheres. The atmospheric corrosion of zinc has been studied in field exposures as well …     

Effect of additive on corrosion resistance of NiFe2O4 ceramics as inert anodes

In order to improve the corrosion resistance of NiFe2O4 ceramics as inert anode, additive V2O5 was added to raw materials NiO and Fe2O3. The inert anodes of nickel-ferrite ceramics were prepared by powder metaUurgic method and the static corrosion rate in Na3AlF6-Al2O3 was determined by mass loss measurement. The effect of V2O5 on sintering property and corrosion resistance was studied. The results show that V2O5 can promote the grain to develop completely and improve sintering property. EDS results show the reaction product Ni2FeVO6 distributes along the grain boundary. The corrosion tests show that V2O5 is beneficial to improving corrosion resistance remarkably. The reasons that V2O5 can improve the corrosion resistance must be V2O5 promoting the gains to develop completely and Ni2FeVO6 distributes along the grain boundary. The stable structure can control the chemical dissolution of ceramics anode and the reinforced grain boundary can control the grain-boundary corrosion rate.     

Microstructural and aqueous corrosion aspects of laser-surface-melted type 304 SS plasma-coated mild steel

Plasma spray deposition of metals, ceramics, or plastics onto base metals to produce wear- and corrosion-resistant surfaces is a promising technique whereby base metal performance can be considerably im-proved. Because these coatings invariably contain pores, voids, and cracks, laser surface melting may be employed to improve their homogeneity. This study focuses on the corrosion performance of laser- sur-face- melted type 304 SS plasma- coated mild steel specimens. Mild steel strips were plasma coated with an approximately 100 to 200 μm thick layer of type 304 by transferred plasma jet. These specimens were sub-sequently laser irradiated using a 3 kW continuous- wave CO₂ gas laser. Eight different sets of specimens were selected based on different laser beam travel speeds. Scanning electron microscopic studies of the plasma- coated specimens revealed both pancake and flowery types of deposited particles. Optical micro-scopic studies followed by anodic polarization experiments were carried out on these specimens in IN H₂SO₄ medium. It was observed that specimens with laser beam interaction times ranging from 30 to 120 ms showed relatively better general corrosion performance than specimens with interaction times of from 15 to 24 ms.