News & Views, Volume 51 | Materials Lab Featured Damage Mechanism
PITTING CORROSION IN CONVENTIONAL FOSSIL BOILERS AND COMBINED CYCLE/HRSGS
By: Wendy Weiss
Pitting is a localized corrosion phenomenon in which a relatively small loss of metal can result in the catastrophic failure of a tube. Pitting can also be the precursor to other damage mechanisms, including corrosion fatigue and stress corrosion cracking. Pits often are small and may be filled with corrosion products or oxide, so that identification of the severity of pitting attack by visual examination can be difficult.
Mechanism
Pitting is a localized corrosion attack involving dissolution of the tube metal surface in a small and well-defined area. Pitting corrosion can occur in any component in contact with water under stagnant oxygenated conditions. Pitting in economizer tubing is typically the result of poor shutdown practices that allow contact with highly-oxygenated, stagnant water. Pitting also may occur in waterwall tubing as a result of acidic attack stemming from an unsatisfactory chemical cleaning or acidic contamination.
Pits that are associated with low pH conditions tend to be numerous and spaced fairly close together. The pits tend to be deep-walled compared to the length of the defect. A breakdown of the passive metal surface initiates the pitting process under stagnant oxygenated conditions. A large potential difference develops between the small area of the initiated active pit (anode) and the passive area around the pit (cathode). The pit will grow in the presence of a concentrated salt or acidic species. The metal ion salt (M+A-) combines with water and forms a metal hydroxide and a corresponding free acid (e.g., hydrochloric acid when chloride is present). Oxygen reduction at the cathode suppresses the corrosion around the edges of the pit, but inside the pit the rate of attack increases as the local environment within the pit becomes more acidic. In the event that the surfaces along the walls of the pit are not repassivated, the rate of pit growth will continue to increase since the reaction is no longer governed by the bulk fluid environment. Pitting is frequently encountered in stagnant conditions that allow the site initiation and concentration, allowing the attack to continue.
By: Wendy Weiss
Structural Integrity (SI)
Industry experience shows that waterwall tubing in conventional boilers can be susceptible to fireside corrosion, depending on fuel type, firing practice, etc. In boilers where fireside corrosion has been identified as a maintenance issue, wastage rates of 5 to 25 mils/year are not uncommon. Since the mid 1990s, the installation of low NOx burner systems designed to lower NOx emissions has significantly increased the wastage rates in some boilers. Operators of subcritical boilers have reported wastage rates as high as 30 mils/year, while those operating supercritical boilers have reported rates exceeding 100 mils/year in the worst cases. These higher damage rates have resulted in an increase in tube failures, and operators have struggled to accurately define the extent of the damage and install the appropriate mitigating technologies.
Structural Integrity (SI) was recently asked to examine a fractured thermowell and determine the damage mechanism.
Acid dewpoint corrosion can occur in conventional and HRSG units in locations where temperatures fall below the sulfuric acid dewpoint temperature. This can occur when either the tube metal temperatures are below the acid dewpoint so that condensate forms on the metal surface, or when flue gas temperatures are below the acid dewpoint, so that the condensate will form on fly ash particles.
