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STEPHEN M. McINTYRE
Ashland Water Technologies Division of Ashland Inc. One Drew Plaza Boonton, New Jersey 07005
2006, Ashland
INTRODUCTION
Corrosion damage leads to untimely production upsets, costly equipment failures and lost opportunities Failure analysis an effective tool in establishing true root cause of failure Root cause determination provides a path to effective corrective actions Common corrosion mechanisms and case histories presented
MECHANISMS
Overheating
Short Term Long Term
Hydrogen Damage Caustic Gouging Oxygen Attack Thermal Fatigue Flow Assisted Corrosion
CASE HISTORIES
Thermal Oxidation Process Upsets in 650 psig HRSG Acrylic Acid Thermo Siphon Steam Generator System Under Deposit Corrosion from Inadequate Precleaning Procedures and Operational Issues
Microstructure consists of bainite or martensite and ferrite Indicates rapid cooling from above eutectoid temperature of 1340 F
Little to moderate bulging Little to moderate reduction in wall thickness Typically accompanied by thermal oxidation Found in superheaters, reheaters, waterwalls
Graphitization
Creep Voids
OVERHEATING Contd
Larson-Miller Parameter: P = T (20 + Log t) Where: P = Larson-Miller parameter T = Temperature of tube metal, degrees Rankine, (F + 460) t = Time for rupture, hours
HYDROGEN DAMAGE
Typically occurs:
Waterwall tubes above operating 1000 psig Beneath heavy deposits Where corrosion releases atomic hydrogen
4NaOH + Fe3O4 2NaFeO2 + Na2FeO2 + 2H2O Fe + 2NaOH Na2FeO2 + 2H 4H+ + Fe3C CH4 + 3Fe
Microstructure exhibits:
Short discontinuous intergranular cracks Decarburization
CAUSTIC GOUGING
Caustic concentrates - DNB or steam blanketing NaOH beneath deposits destroys protective magnetite film NaOH corrodes base metal Also, evaporation along waterline with no deposits
OXYGEN ATTACK
Dissolved O2 yields cathodic depolarization Reddish-brown hematite (Fe2O3) or rust deposits or tubercles Hemispherical pitting beneath deposits
THERMAL FATIGUE
Numerous cracks and crazing, oxide wedge Caused by: Excessive cyclic thermal fluctuations Excessive thermal gradients and mechanical constraint DNB or rapidly fluctuating flows in waterwalls Low-amplitude vibrations of entire superheaters
Localized thinning Dissolution of protective oxide and base metal Occurs in single or two phase water Low pressure system bends in evaporators, risers and economizer tubes Feedwater cycle (due to more volatile chemistry and lower pH)
1.0 0.8 0.6 0.4 0.2 0.0 100 150 200 250 300 350 400 450 500 550
Temperature (0F)
30
20
10
pH has significant effect on normalized wear rate of carbon steel Nearly forty (40) fold reduction between pH 8.6 and 9.4
25 20 15 10 5 0 0 10 20 30 40 50 60 70 80 90 100
Dissolved oxygen has direct impact FAC minimized above 30 ppb O2 FAC increases exponentially below 30 ppb O2
Velocity (ft/sec)
Normalized wear rate minimal below 10 ft/sec Rate increases by 2.8 times at 100 ft/sec
Geometry affects location of FAC, regardless of Reynolds Number Changes in flow rate may not significantly reduce FAC
East
10
15
20
25
30
40
45
50
55
Bottom/left photo illustrates the tubes cross-section, which revealed a layered, brittle oxide layer that measured 0.142.
ID (waterside) surface of failed tube (smooth finned) as split, which revealed heavy accumulation of reddish-black, scab-like deposit and corrosion product. Visible gouging damage and failure also observed.
Through-wall gouging
ID (waterside) surface after cleaning. Note severe, localized gouging beneath deposits. Copper corrosion products also observed near gouged areas.
Close up view of copper corrosion products observed near gouged area of smooth finned tube.
Photomicrograph of copper corrosion products dispersed throughout iron oxide matrix at ID surface.
Photomicrograph of tube metal microstructure at gouged area. Microstructure consists of normal lamellar pearlite and ferrite. Nital Etch Magnification 855 X
ID (waterside) surface of serrated-fin tube with localized accumulation of adherent, scab-like, rusty brown corrosion products.
Chemical Analysis of water soluble components from the iron oxide deposit at base metal interface of tube. CHN-S testing performed on bulk dry deposit (not water extract).
Sulfate Chloride Sodium Silicon Calcium (as Ca) Magnesium (as Mg) Iron Copper Barium Potassium CHN-S Testing Carbon Hydrogen Nitrogen Sulfur 0.7% 0.2% <1.0% <1.0% 9,039.7 g/gm 132 g/gm 344.2 g/gm 119.2 g/gm 3257 g/gm 63.7 g/gm <5.0 g/gm 221.8 g/gm 66.2 g/gm 625.6 g/gm
ID (waterside) surfaces of adjacent unfailed tubes exhibited thin, non-magnetic, reddish deposit layer. DWD measured 5.2 g/ft2. Remaining tubes were essentially free of corrosion and in excellent condition.
Failure Mechanism
Thermal excesses and/or inadequate flow led to DNB/steam blanketing .
Failure Mechanism
Failure Mechanism
Thermal excesses and/or inadequate flow led to DNB/steam blanketing . Scab-like deposits formed. Anions concentrated beneath iron deposits and created a corrosive environment. Tubes thinned as a result of corrosion. Internal pressure overcame the thinned tube wall.
Install baffles or orifices to improve flow to center tubes Install a central downcomer Ensure that finned tubes are situated appropriately Stagger tubes rather than positioning them in-line
Coordinated Phosphate approach Phosphate ion will assist in buffering corrosive environment beneath deposits AVT maintained in salt coolers
Localized pitting Shallow corrosion Maximum penetration (0.031) 36% wall loss Undercut pitting suggests an acid form of attack
Preferential attack of welded seam observed Specifically at expanded end Maximum penetration (0.029) 34% wall loss
Very thin, non-uniform black oxide and flash rust Oxide scale thickness ranged 0.0006 to 0.0010 DWD measured 4.9 g/ft2
Bare shiny metal at localized pitting attack Shot blasted appearance at freshly exposed metal Note cracked and crazed pattern in oxide scale
Magnification 113 x
Magnification 177 x
Iron 84.8% Oxygen 13.2% Calcium 0.74% Sulfur 0.35% Phosphorus 0.34% Silicon 0.27% Chlorine 0.27% Elemental Analysis at Pitted Area
Root Cause(s):
Alloy substitution of plug in upstream unit H2SO4 Black Acid upstream process leaked into condensate used for boiler feedwater No response to on-line conductivity warnings Contaminated condensate not dumped Boiler operated at pH 2-3 for several days
Corrective Actions:
Water no longer considered a utility, but rather a part of the process Best practice and process control measures implemented Re-educated operators Automated dump station activated by low feedwater pH No subsequent tube failures in four years
CASE HISTORY #3
Under Deposit Corrosion
Cogeneration HRSG System 1800 psig High Pressure Evaporator Unit Approximately 4000 hours (5.5 months) Congruent phosphate, organic oxygen scavenger, neutralizing amines Tube material: SA-178 D (2 tubes received) Failures occurred in first row, center section of the HP evaporator, facing gas path Organic acid process contamination in makeup Misaligned duct burners also reported
Laboratory Examination:
Alloy Analysis:
Tube No. 13 Tube No. 81 SA-178 Gr. D
Laboratory Examination:
Visual Inspection
Thick adherent oxide on hot side Severe gouging Trace white deposits at oxide tube interface No maricite layer
Cracking
Laboratory Examination:
Visual Inspection
Gouge along hot side away from failure No gray-white maricite layer observed Dry grind to minimize loss of water soluble deposits
Laboratory Examination:
SEM-EDS
Laboratory Examination:
Microstructure
Preferential attack at weld seam Weld not normalized In-situ spheroidization No decarburization observed
Laboratory Examination:
Microstructure
Several inches away (in line) from failure Intergranular cracking at gouged area Hydrogen induced crack at ERW seam Characteristic of SCC in carbon steel
Laboratory Examination:
Microstructure
Numerous intergranular cracks at gouged area Cracking is typical of hydrogen damage Slight in-situ spheroidization around entire circumference
Laboratory Examination:
Microstructure (Separate tube)
Microstructure at gouged area exhibited iron carbide transformation product, or Widmansttten structure, indicating rapid cooling from above eutectoid transformation temperature of 1340 F
Laboratory Examination:
Key Observations
Severe gouging along hot side of tube Heavy magnetite deposit (corrosion product) Distinct maricite (NaFePO4) layer not observed No evidence of Cl or SO4 observed at interface Hydrogen induced cracking at gouge and ERW Very high peak metal temperatures reached Insufficient sample received to evaluate true internal cleanliness Elemental deposit analysis alone does not identify specific corrosion products Attack more closely resembles caustic gouging and SCC Requested adjacent unfailed tube and >24 hours to conduct lab exam
Laboratory Examination:
Follow-up Tube Analysis
Hot Side Back Side
Adjacent tube received one month later Distinct waterline marking along hot side Reddish-black friable deposits Internal DWD (g/ft2): 13.1 hot side, 9.1 back side
Laboratory Examination:
Follow-up Tube Analysis (Contd)
Laboratory Examination:
Follow-up Tube Analysis (Contd)
Hot Side
Cold Side
Laboratory Examination:
Follow-up Tube Analysis (Contd)
Adjacent Tube: Normal lamellar pearlite and ferrite microstructure observed around entire circumference. No evidence of cracking, decarburization or any other forms of degradation observed throughout entire tube. Nital Etch Magnification 500 x
Field Examination:
Follow-up Tube Analysis (Contd)
Video probe view of identical tubes in adjacent unfired HRSG unit. No pre-cleaning performed.
Internal rust and non-protective oxides will enhance wick boiling and under deposit forms of attack, especially in high heat flux zones.
CASE HISTORY #3
Conclusions
Failures do not always exhibit a single classic mechanism Careful coordination required between laboratory examination, field inspection, and operating records Failure attributed to under deposit corrosion Caustic corrosion and hydrogen induced SCC primary corrosion mechanism(s)
CASE HISTORY #3
Leading Causes of Under Deposit Corrosion
Localized Departure from Nucleate Boiling (DNB) Localized and very high heat flux from misaligned duct burners BFW upsets from process contamination and demineralizer control Pre-existing deposits from construction and outside storage of tubes No pre-cleaning prior to commissioning
CASE HISTORY #3
Corrective Actions
Changed treatment program from congruent to equilibrium PO4 to offer improved buffering against organic acid process contamination Improved demineralizer system to minimize over runs Recommended precleaning tubes prior to start up
2006, Ashland