Comprehensive investigation of the corrosion state and surface properties of the stainless steel tubes of steam generators

Evaluating the water chemistry in the primary circuit and the effect of chemical econtamination of the heat exchanger tubes performed by the AP-CITROX (AP: alkaline permanganate; CITROX: citric and oxalic acid) procedure at Paks NPP (Hungary), a project dealing with the comprehensive investigation of the general corrosion state of the steam generators (SGs) has been initiated. Owing to the fact that there is no investigation method available for the in-situ monitoring of the inner surfaces of heat exchanger tubes, a research program based on sampling as well as on ex-situ electrochemical (voltammetric) and surface analytical measurements (SEM-EDX, CEMS, XRD, XPS) was developed and elaborated. In the time period of 2000-2008 - within the frame of the above project - 45 stainless steel specimens, cut out from various locations of the steam generators of the Paks NPP were investigated. Based on the measured corrosion characteristics (corrosion rate, thickness and chemical composition of the protective oxide-layer) it was found that these parameters are strongly dependent on the decontamination history of steam generators. The present work gives a brief overview on the general corrosion state of the heat exchanger tubes of SGs, concerning the long-term effects of the AP-CITROX procedure on the chemical composition and structure of the protective oxide-layer.

Free fatty acid influenced corrosion inhibition mechanisms of some inedible plants seeds oils on low alloyed medium-carbon steel in H2SO4

Purpose The purpose of this paper is to investigate the mechanisms of low alloyed medium-carbon steel (LAMCS) corrosion in 0.5 M H2SO4 inhibited by seeds oils of rubber (SOR), Neem (SON) and Jatropha (SOJ) containing varying degree of free fatty acid (FFA). Design/methodology/approach Specific gravity, acid values and FFA compositions of oils were determined. Potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and X-ray diffraction (XRD) are techniques used to investigate the corrosion inhibition mechanisms with evaluated Gibbs free energy of adsorption. Findings Corrosion inhibition efficiencies of oils reached values >99% as obtained from PDP and EIS. Protective oxide layer was formed on LAMCS consequent on containment of carbonyl and hydroxyl groups in the FFA of SOR, SON and SOJ, respectively. The SOR and SOJ are found to be mixed inhibitors, whereas SON behaved as anodic inhibitor. Mechanism of adsorption of SOR was synergistic between physisorption and chemisorption, while SON and SOJ exhibited physisorption. SEM micrographs images showed that uninhibited sample exhibited thicker mass of corrosion products. Formation of protective oxide layer was confirmed by XRD diffractograms. Practical implications This study has shown that the need for modification of vegetable seed oils containing FFA is unnecessary as the hydroxyl and carbonyl groups of the FFA contained in the respective oil were found to be the center of adsorption of the oils on the steel surface. Hence, cost and by-products associated with modification of oils used as corrosion inhibitors are eliminated. Originality/value SOR, which has the highest percentage FFA, was found to be the most influential on the corrosion inhibition mechanism of LAMCS, specifically within 0.01–0.02 g/mL concentration. FFA contained in the respective seed oil aided formation of protective oxide layer at interface between H2SO4 and LAMCS, relative to amount composed.

Oxidation of Metals

Oxides are formed on the surfaces of most metals we use today when they are exposed to an environment suitable for oxidation. The formation of these oxides usually has negative effects that cause severe corrosion problems detrimental to the operation of electronic devices, but it can also have positive effects in that a protective oxide layer that prevents further penetration of oxygen into the material may be formed. Therefore, understanding the effect of oxidation in metals plays an important role in the advancement of modern science and technology. In this paper, we will review the conventional theory of oxidation and present a state-of-the-art model of oxidation based on recent discoveries.

Surface Modification on Ti-6Al-4V Alloy During Corrosion in a High Temperature Ionic Liquid

Corrosion behavior of Ti-6Al-4V alloy was investigated by anodic polarization curves in LiF-NaF-KF molten salts mixture at 823K. The surface alloy (native composition and its modification and corrosion resistance after 4 hours immersion) was studied by XRD, SEM and XPS. XPS analysis shows TiO2 with small amount of V2O5, Al2O3 and TiF4, while in the electrolyte it was showed the presence of V in a very low concentration. AFM demonstrates that formation of a rough and non-protective oxide layer should be responsible for the weak protective properties of the alloy. The degradation mechanism of the alloy during corrosion is based on the formation of TiF4 and of the passing of vanadium in the molten electrolyte.

Effect of Drum Pressure on Flow Accelerated Corrosion in Gas Fired Combined Cycle Power Plant: A Case Study and Literature Review

The dissolution of ferrous ions from the protective oxide layer and/or base metal by corrosion with the assistance of turbulent flow is called flow accelerated corrosion (FAC). Flow accelerated corrosion is the most common and continuous corrosion reaction in combined cycle power plants (CCPP). Heat recovery steam generator (HRSG) drum pressure fluctuation and/or turbulent drum water greatly influences the FAC of drum and economizer. This kind of FAC was investigated in the low-pressure drum (LPD) and low-pressure economizer (LPE) of a 210 MW gas-fired combined cycle power plant (Four-unit HRSG & GT) with an air-cooled condenser (ACC). Severe FAC was observed due to the fluctuation of pressure in the LPD with respect to time. As a result, huge amounts of soluble iron (Fe2+) and insoluble (Fe3+) was found in all running HRSG’s LPD water. Due to pressure fluctuations in the LPD, a protective oxide layer (mostly magnetite), as well as the base metal, were corroded from the LPD and LPE even after carefully maintaining recently developed water cycle chemistry in this CCPP. Severe leakage was found in the LPE due to corrosion. The actual reason for the problem was found to be a malfunctioning steam-control valve in the turbine unit’s LP system. This valve was malfunctioning by suddenly opening to 100% and then closing to around 10% continuously. This malfunction creates enormous pressure drops in both the LPD and LPE units. It is understood that water turbulence is the main cause of FAC affecting the LDP and LPE. This assessment is based on chemical laboratory analysis and physical inspection. There was no non-destructive testing (NDT) performed in this study. The severe FAC happened in four days and for this reason, HRSG and steam turbines were shut down. Maintenance work on the control valve and flushing of the LPD and LPE successfully resolved the FAC problem. One week later, LPE leakage was found on the unit-3 HRSG and as reported in this study this was also found to be the result of FAC. From this case study, it is concluded that not only water quality but also water turbulence can create severe FAC problem.

High-Temperature Oxidation Behavior and Kinetics of Forged 12Cr-MoVW Steel

The oxidation kinetics of forged 12Cr-MoVW steel was investigated in an air (N2+O2) atmosphere at 873-1073 K (Δ50 K) using thermogravimetric analysis. The oxidized samples were characterized using X-ray diffraction, and the surface and cross-sectional morphologies were examined using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The forged 12Cr-MoVW steel samples exhibited parabolic behavior and a low oxidation rate compared with their as-cast counterparts. A protective oxide layer was uniformly formed at relatively low temperature (≤973 K) for the forged samples, which thus exhibited better oxidation resistance than the as-cast ones. These oxides are considered solid-solution compounds such as (Fe, Cr)2O3.