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 – Cont’d.

• Microstructure consists of bainite or martensite and ferrite

• Indicates rapid cooling from above eutectoid temperature of 1340 ºF
SHORT TERM OVERHEATING – Cont’d

• 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 - Cont’d

Normal Pearlite and Ferrite Microstructure

LONG TERM OVERHEATING - Cont’d

In-situ spheroidization of iron carbides

LONG TERM OVERHEATING - Cont’d

Complete spheroidization of iron carbides

LONG TERM OVERHEATING - Cont’d

Graphitization
LONG TERM OVERHEATING - Cont’d

Creep Voids
LONG TERM OVERHEATING - Cont’d

• 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 ºF for carbon steel)
OVERHEATING – Cont’d
Larson-Miller Parameter:

P = T (20 + Log t)

Where: P = Larson-Miller parameter

T = Temperature of tube metal,
degrees Rankine, (ºF + 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 – Cont’d
Concentrated Sodium Hydroxide Mechanism:

4NaOH + Fe3O4 →
2NaFeO2 + Na2FeO2 + 2H2O

Fe + 2NaOH → Na2FeO2 + 2H

4H+ + Fe3C → CH4 + 3Fe

HYDROGEN DAMAGE – Cont’d

• Thick-lipped
• Brittle appearance
• Window sections (sometimes) blown out
HYDROGEN DAMAGE – Cont’d

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 – Cont’d

• FAC affected by:

– Temperature
– pH
– O2 concentration
– Mass flow rate
– Geometry
– Quality of fluid
– Alloys of construction
FLOW ASSISTED CORROSION – Cont’d
1.2

1.0
Noralized Wear Rate

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 ºF

 FLOW ASSISTED CORROSION – Cont’d
40
Normalized Wear Rate
30

20

10

0
8.6 8.8 9.0 9.2 9.4
pH

• 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 – Cont’d
35

30
Noralized Wear Rate
25

20

15

10

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 – Cont’d
2.8

Noralized Wear Rate 2.6

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 – Cont’d
Wear due to
Secondary
Wear at Flow at
Low Re Medium Re
Numbers Numbers

Wear at
High Re
Numbers

• Geometry affects location of FAC, regardless of Reynold’s Number

• Changes in flow rate may not significantly reduce FAC
FLOW ASSISTED CORROSION – Cont’d

• 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

5 10 15 20 25 30 35 40 45 50 55
Fire Box Side

Failed
Scale detected
Borescoped - Clean
Operating Conditions-Video Probe View

Notice iron oxide film

has been compromised
Operating Conditions-
Visual 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 tube’s 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 9,039.7 µg/gm
Chloride 132 µg/gm
Sodium 344.2 µg/gm
Silicon 119.2 µg/gm
Calcium (as Ca) 3257 µg/gm
Magnesium (as Mg) 63.7 µg/gm
Iron <5.0 µg/gm
Copper 221.8 µg/gm
Barium 66.2 µg/gm
Potassium 625.6 µg/gm
CHN-S Testing
Carbon 0.7%
Hydrogen 0.2%
Nitrogen <1.0%
Sulfur <1.0%
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 Mechanism-
Failed Tube Orientation
 Failure Mechanism-
Operating 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 Mechanism-
Operating 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 78.8% Iron 69.6%

Oxygen 18.7% Oxygen 13.8%
Sulfur 0.74% Calcium 9.70%
Silicon 0.67% Phosphorus 4.00%
Calcium 0.57% Copper 2.30%
Chlorine 0.42% Sulfur 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 0.20 0.20 0.27 max.

% Manganese 1.26 1.31 1.00-1.50

% Phosphorus 0.011 0.012 0.030 max.

% Sulfur 0.003 0.003 0.015 max.

% Silicon 0.16 0.25 0.10 min.

Laboratory Examination:
Visual Inspection

• Thick adherent oxide on hot

side
• Severe gouging
• Trace white deposits at Cracking
oxide tube interface
• No maricite layer
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

Phosphorus 20.1%
Manganese 18.3%
Sodium 16.0%
Iron 11.6%
Analysis of deposits at Silicon 3.5%
Aluminum 1.0%
oxide-metal interface Calcium 0.3%
Oxygen 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 Widmanstätten structure, indicating rapid cooling from
above eutectoid transformation temperature of 1340 ºF
 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 (Cont’d)

Iron 83.6%
Manganese 1.3%
SEM-EDS Analysis of
Aluminum 0.5%
reddish-black deposits
Phosphorus 0.4%
on ID surface of
Calcium 0.3%
adjacent tube
Oxygen 14.0%
Laboratory Examination:
Follow-up Tube Analysis (Cont’d)
Hot Side

Adjacent Tube: Cold Side

Internal appearance after
glass bead blasting
 Laboratory Examination:
Follow-up Tube Analysis (Cont’d)

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 (Cont’d)

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