BOILER TUBE FAILURES Things Your Father May Not Have Told You

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

SHORT TERM OVERHEATING

Thin-lipped, longitudinal rupture Extensive tube bulging Large fish-mouth appearance

SHORT TERM OVERHEATING Contd.

Microstructure consists of bainite or martensite and ferrite Indicates rapid cooling from above eutectoid temperature of 1340 F

SHORT TERM OVERHEATING Contd

Typical Causes:
Low water level Partial or complete pluggage of tubes Rapid start-ups Excessive load swings Excessive heat input

LONG TERM OVERHEATING

Little to moderate bulging Little to moderate reduction in wall thickness Typically accompanied by thermal oxidation Found in superheaters, reheaters, waterwalls

LONG TERM OVERHEATING - Contd

Normal Pearlite and Ferrite Microstructure

LONG TERM OVERHEATING - Contd

In-situ spheroidization of iron carbides

LONG TERM OVERHEATING - Contd

Complete spheroidization of iron carbides

LONG TERM OVERHEATING - Contd

Graphitization

LONG TERM OVERHEATING - Contd

Creep Voids

LONG TERM OVERHEATING - Contd

Typical causes:
Gradual accumulation of deposits or scale Partially restricted steam or water flow Excessive heat input from burners Undesired channeling of fireside gases Steam blanketing in horizontal or inclined tubes Operation slightly above oxidation limits of given tube steel (850 F for carbon steel)

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

HYDROGEN DAMAGE Contd

Concentrated Sodium Hydroxide Mechanism:

4NaOH + Fe3O4 2NaFeO2 + Na2FeO2 + 2H2O Fe + 2NaOH Na2FeO2 + 2H 4H+ + Fe3C CH4 + 3Fe

HYDROGEN DAMAGE Contd

Thick-lipped Brittle appearance Window sections (sometimes) blown out

HYDROGEN DAMAGE Contd

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

FLOW ASSISTED CORROSION

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)

FLOW ASSISTED CORROSION Contd

FAC affected by:

Temperature pH O2 concentration Mass flow rate Geometry Quality of fluid Alloys of construction

FLOW ASSISTED CORROSION Contd

1.2

Noralized Wear Rate

1.0 0.8 0.6 0.4 0.2 0.0 100 150 200 250 300 350 400 450 500 550

Temperature (0F)

Greatest potential for FAC occurs around 300 F

FLOW ASSISTED CORROSION Contd

40 Normalized Wear Rate

30

20

10

0 8.6 8.8 9.0 pH 9.2 9.4

pH has significant effect on normalized wear rate of carbon steel Nearly forty (40) fold reduction between pH 8.6 and 9.4

FLOW ASSISTED CORROSION Contd

35 30

Noralized Wear Rate

25 20 15 10 5 0 0 10 20 30 40 50 60 70 80 90 100

Oxygen Concentration (ppb)

Dissolved oxygen has direct impact FAC minimized above 30 ppb O2 FAC increases exponentially below 30 ppb O2

FLOW ASSISTED CORROSION Contd

2.8 2.6

Noralized Wear Rate

2.4 2.0 1.8 1.6 1.4 1.2 1.0 10 20 30 40 50 60 70 80 90 100

Velocity (ft/sec)

Normalized wear rate minimal below 10 ft/sec Rate increases by 2.8 times at 100 ft/sec

FLOW ASSISTED CORROSION Contd

Wear at Low Re Numbers Wear due to Secondary Flow at Medium Re Numbers

Wear at High Re Numbers

Geometry affects location of FAC, regardless of Reynolds Number Changes in flow rate may not significantly reduce FAC

FLOW ASSISTED CORROSION Contd

Most often found in all-ferrous metallurgy 0.1% addition of chromium can reduce FAC Trace levels of chromium in low carbon steels (like SA-178 or SA-210) provide benefits, even though chromium content not specified.

CASE HISTORY #1:

THERMAL OXIDIZER BOILER TUBE FAILURES Maleic Unit Thermal Oxidizer Boiler 650 psig 12 years old All volatile treatment (AVT) Fired by natural gas and waste solvent streams SA-192 tube material (low carbon steel)

Map of Tube Failures

Economizer side

East

10

15

20

25

30

35 Fire Box Side

40

45

50

55

Failed Scale detected Borescoped - Clean

Operating Conditions-Video Probe View

Notice iron oxide film has been compromised

Operating ConditionsVisual Inspection

Notice layered iron oxide chips

As-Received for Laboratory Examination

Figure 1: Top/right photo shows the finned tube specimen as received from row 17, which exhibited a complete wall failure at the external radius of the bend.

Bottom/left photo illustrates the tubes cross-section, which revealed a layered, brittle oxide layer that measured 0.142.

Magnified view of oxide layer shown in Figure 1 (bottom photo) Magnification 5X

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.

Note waterline marks

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.

Failure MechanismFailed Tube Orientation

Failure MechanismOperating Conditions

Gas side temperature increases reduce mean time to failure Pressure fluctuations cause significant increase in steam volume Potential exists for overheating due to steam stalling Boiler operated at maximum (and beyond) capacity Finned tubes installed 1 to 2 rows in front of design location

Failure MechanismOperating Conditions

Thermal cycling disrupts iron oxide film Spalled iron oxide accumulates further down in tubes Boiler water penetrates chip scale Wick boiling concentrates boiler water solids to percent levels Tube wall thinning results from over concentration of solids and acid attack due to hydrolysis by Cl or SO4 anions Maximum allowable stress is exceeded due to thinning

Corrective Actions & Recommendations

Improve boiler circulation Control intrusion of corrosive anions Maintain a buffering chemistry in the boiler water Modify boiler operation to avoid DNB

Corrective Actions & Recommendations Improve Circulation

Points to be explored with the Boiler Manufacturer:

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

Corrective Actions & Recommendations Eliminate Corrosive Anions

Identify sources of BFW contamination
Analyze component streams Sentry sampler for low level metals analysis Eliminate or purify contaminated stream(s)

Polish BFW components

Makeup Condensate

Consider chemical cleaning

Corrective Actions & Recommendations Monitor BFW Quality

Install Online Analyzers

Cation Conductivity pH

Corrective Actions & Recommendations Buffering Chemistry

Coordinated Phosphate approach Phosphate ion will assist in buffering corrosive environment beneath deposits AVT maintained in salt coolers

CASE HISTORY #2:

SALT COOLER TUBE FAILURES Salt Cooler Thermo Siphon Steam Generator Molten NaCl heat source Operating pressure: 600 psig 15 years old Coordinated PO4 and amines Periodic upsets in O2 control Tubes: SA-214 (low carbon steel) 165 failed tubes in acrylic acid unit $50 MM in damages and lost opportunities

Cleaned Tubes (As Received)

Localized pitting Shallow corrosion Maximum penetration (0.031) 36% wall loss Undercut pitting suggests an acid form of attack

Cleaned Tubes (As Received)

Preferential attack of welded seam observed Specifically at expanded end Maximum penetration (0.029) 34% wall loss

Uncleaned Tubes (As Received)

Very thin, non-uniform black oxide and flash rust Oxide scale thickness ranged 0.0006 to 0.0010 DWD measured 4.9 g/ft2

Uncleaned Tubes (SEM-EDS)

Iron Oxygen Sulfur Silicon Calcium Chlorine

78.8% 18.7% 0.74% 0.67% 0.57% 0.42%

Iron Oxygen Calcium Phosphorus Copper Sulfur

69.6% 13.8% 9.70% 4.00% 2.30% 0.48%

Black oxide scale

Orange-brown and black oxide scale corrosion products

Uncleaned Tubes (Stereoscopic View)

Bare shiny metal at localized pitting attack Shot blasted appearance at freshly exposed metal Note cracked and crazed pattern in oxide scale

Uncleaned Tubes (SEM-EDS)

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

% Carbon % Manganese % Phosphorus % Sulfur % Silicon

0.20 1.26 0.011 0.003 0.16

0.20 1.31 0.012 0.003 0.25

0.27 max. 1.00-1.50 0.030 max. 0.015 max. 0.10 min.

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

Analysis of deposits at oxide-metal interface

Phosphorus Manganese Sodium Iron Silicon Aluminum Calcium Oxygen

20.1% 18.3% 16.0% 11.6% 3.5% 1.0% 0.3% 29.0%

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)

SEM-EDS Analysis of reddish-black deposits on ID surface of adjacent tube

Iron Manganese Aluminum Phosphorus Calcium Oxygen

83.6% 1.3% 0.5% 0.4% 0.3% 14.0%

Laboratory Examination:
Follow-up Tube Analysis (Contd)
Hot Side

Adjacent Tube: Internal appearance after glass bead blasting

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