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

Noralized Wear Rate

1.2
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

Normalized Wear Rate

40

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

Noralized Wear Rate

30
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

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 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

Failed
Scale detected
Borescoped - Clean

15

20

25

30

35
Fire Box Side

40

45

50

55

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

9,039.7 g/gm

Chloride

132 g/gm

Sodium

344.2 g/gm

Silicon

119.2 g/gm

Calcium (as Ca)

3257 g/gm

Magnesium (as Mg)

63.7 g/gm

Iron

<5.0 g/gm

Copper

221.8 g/gm

Barium

66.2 g/gm

Potassium

625.6 g/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 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%

Black oxide scale

Iron
Oxygen
Calcium
Phosphorus
Copper
Sulfur

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

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
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