Under What Specific Combination of High pH (>9.5) and High Temperature (>150 graden) Gaat de 316L verwarmingsmantel over van passieve naar actieve corrosie via chroomhydroxidecomplexatie in ontlucht water

PASSIVITY BREAKDOWN MECHANISM IN DEAERATED HIGH TEMPERATURE HIGHLY ALKALINE ENVIRONMENTS In high pH boiler feedwater (pH>9.5 at operating temperature, deaerated) such as high pressure boiler economiser or nuclear reactor auxiliary cooling with alkaline water chemistry at temperatures >150°C the passive film on 316L stainless steel sheathed electric heating tubes changes from a protective chromium(III) oxide/hydroxide to soluble chromite (CrO2-) species. This is known as caustic gouge or alkaline corrosion and results in rapid, homogenous loss of metal. This is the general corrosion due to the solubility of the passive coating and does not require applied stress as in the case of caustic stress corrosion cracking (CSCC). The corrosion rate is an exponential increasing function for pH > 9.5 and temperature > 150°C (measured at room temperature). Corrosion rates are 0.2-0.5 mm/year at pH 10.0, 200 deg C. Rates >1-2 mm/year at 250°C and pH 10.5. The attack can be averted by the addition of silicates or phosphates (common boiler water treatments) which form protective layers. In this paper, we quantify the limit in pH-temperature for the transition passive to active in deaerated alkaline high temperature water. Mechanism of Complex Formation of Chromium Hydroxide The passive film on 316L in high temperature water is a bilayer with an inner Cr2O3 layer and an outside Fe3O4/FeCr2O4 layer. Chromium oxide is soluble at high pH (>9.5) by formation of chromite ions: Cr2O3 + 2OH- ->2CrO2- + H2O De snelheid van deze reactie is afhankelijk van de temperatuur en de concentratie van OH- . Onder ontluchte omstandigheden (opgeloste zuurstof<10 ppb) there is no competing cathodic activity to repair the passive layer and the dissolution is uniform. At high pH the iron oxides are also soluble, forming ferrite (FeO2 2-) and ferrates (FeO4 2-). Which leads to active, general corrosion , but no pitting or cracking . That is, a thinning of the whole sheath wall. Quantification of pH-Temperature Corrosion Rates in Deaerated Water 316L has been tested in deaerated water (<10 ppb O 2 ) with pH adjusted by NaOH (measured at 25 °C) at various temperatures in a controlled autoclave and the following corrosion rates have been established. pH @ 25°C pH @ Operating Temperature (approx.) Temperature (C) Corrosion Rate (mm/yr, deaerated)Time to Metal Loss 0.2 mm (hrs) Suggested service for Mechanism Dominant >5.000 uur 8.5 7.5-8.0 (<9.5) 150-250 <0.02 >10,000 Passive Yes 9.0-9.5 8.0-9.0 150 0.02-0.05 4,000-10,000 Passive Yes 9.0 - 9.5 8.0-9.0 200 0.05-0.10 2,000-4,000 Acceptable transition 9.0-9.5 8.0-9.0 250 0.10-0.20 1,000-2,000 MarginalNot Recommended 9.5-10.0 9.0-9.5 150 0.05-0.10 2,000-4,000 Good Transition :) 9.5 - 10.0 9.0 - 9.5 180 0.10 - 0.20 1000 - 2000 Active (CrO2-) Not recommended 9.5-10.0 9.0-9.5 200 0.20-0.40 500-1000 Active 10.0-10.5 9.5-10.0 150 0.10-0.20 1,000-2,000 Active Not recommended 10.0-10.5 9.5-10.0 180 0.30-0.60 350-700 Active No 10.0-10.5 9.5-10.0 200 0.50-1.00 200-400 Active No 10.5-11.0 10.0-10.5 120 0.10-0.20 1,000-2,000 Active Not recommended 10.5-11.0 10.0-10.5 150 0.50-1.00 200-400 Active Yes >11.0 >10.5 >100 >1.00 <200 Severe Yes The Effect of Water Treatment Chemicals on Alkaline Corrosion Phosphates (PO₄³⁻) and silicates (SiO₃²⁻) can form protective films to minimise alkaline corrosion. Additive Concentration (ppm) Corrosion Rate Reduction Factor (pH 10.0, 200 °C) Recommended pH limit with additive (200 °C) None 0 1.0× (baseline) 9.0 Sodium phosphate, Na3PO4 5-10 0.3-0.5× 9.5 Phosphate sodium 20-50 0.1-0.2× 10.0 Sodium silicate 5-10 0.5-0.7× 9.5 Sodium silicate 20-50 0.2-0.4× 10.0 Phosphate bound (Na:PO4=2.5-3.0) 10-20 0.1-0.3× 10.5 Practical Recommendations for High-pH Boiler Feedwater Heaters The following pH and temperature limitations apply to 316L encapsulated heaters in deaerated, high pH boiler feedwater systems. Water Treatment for Boilers pH operating (25 °C) Maximum Temperature (°C) over 5 Years Heater Life (years) Expected Heater Life Low pressure (< 5 MPa)Phosphate (complexed) 9.0-9.5 200 8-12 Medium pressure (5-10 MPa)Coordinated Phosphate 9.0–9.5 180 6–10 high pressure (10-15 MPa) AVT (all-volatile, ammonia) 8.5-9.0 200 8-12 High pressure (15-20 MPa) AVT (all volatile ammonia) 8.5-9.0 180 6-10 Very high pressure ( >20 Mpa)Oxygenated therapy (OT) 200 8.0-8.5 >10 (OT) Any pH > 9.5Any >9.5 <150 3-5 (monitor) Alkali Type Field Identification General Corrosion A 316L heater in high pH deaerated high temperature water fails by uniform wall thinning with no pitting or breaking. Surface can be matte, engraved or sandblasted. Corrosion products may be tiny (soluble chromite). Water chemistry log will show pH >9,5-10,0 bij bedrijfstemperatuur De oplossing is om de pH te verlagen naar 8,5-9,0 en fosfaten/silicaten toe te voegen of te vervangen door een legering op nikkelbasis (bijvoorbeeld Alloy 825 of Inconel 600) die beter bestand is tegen alkalische corrosie. Conclusie: Beheers de pH en temperatuur om alkalische corrosie te voorkomen. De pH voor de overgang van passief (corrosiesnelheid<0.02 mm/year) to active alkaline corrosion (0.2-1.0 mm/year) of 316L stainless steel heater sheaths in deaerated high-temperature water is >9.5 at 200°C or >9.0-9.5 at 250°C. If engineers select 316L sheaths for boiler feedwater or high-pH systems, they should maintain the operating pH (measured at 25°C) below 9.5 at temperatures above 150°C. A coordinated phosphate treatment (Na:PO 4 ratio of 2.5-3.0) will reduce the corrosion rate of 316L some 70-90 %. This is for carbon steel protection where pH >9,5 is vereist. Dit raamwerk koppelt uniforme corrosiesnelheden in ontlucht alkalisch water aan pH, temperatuur en waterbehandeling.