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BOILER TUBE FAILURES “ Things Your Father May Not Have Told You” STEPHEN M. McINTYRE

BOILER TUBE FAILURES

Things Your Father May Not Have Told You”

FAILURES “ Things Your Father May Not Have Told You” STEPHEN M. McINTYRE ©2006, Ashland Ashland
FAILURES “ Things Your Father May Not Have Told You” STEPHEN M. McINTYRE ©2006, Ashland Ashland
FAILURES “ Things Your Father May Not Have Told You” STEPHEN M. McINTYRE ©2006, Ashland Ashland

STEPHEN M. McINTYRE

©2006, Ashland
©2006, Ashland

Ashland Water Technologies Division of Ashland Inc. One Drew Plaza Boonton, New Jersey 07005

M. McINTYRE ©2006, Ashland Ashland Water Technologies Division of Ashland Inc. One Drew Plaza Boonton, New
INTRODUCTION • Corrosion damage leads to untimely production upsets, costly equipment failures and lost opportunities

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

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

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
SHORT TERM OVERHEATING
SHORT TERM OVERHEATING • Thin-lipped, longitudinal rupture • Extensive tube bulging • Large fish-mouth appearance

Thin-lipped, longitudinal rupture

Extensive tube bulging

Large fish-mouth appearance

SHORT TERM OVERHEATING – Cont’d.
SHORT TERM OVERHEATING – Cont’d.
SHORT TERM OVERHEATING – Cont’d. • Microstructure consists of bainite or martensite and ferrite • Indicates

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

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
LONG TERM OVERHEATING
LONG TERM OVERHEATING • Little to moderate bulging • Little to moderate reduction in wall thickness
LONG TERM OVERHEATING • Little to moderate bulging • Little to moderate reduction in wall thickness

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
LONG TERM OVERHEATING - Cont’d

Normal Pearlite and Ferrite Microstructure

LONG TERM OVERHEATING - Cont’d
LONG TERM OVERHEATING - Cont’d
LONG TERM OVERHEATING - Cont’d In-situ spheroidization of iron carbides

In-situ spheroidization of iron carbides

LONG TERM OVERHEATING - Cont’d
LONG TERM OVERHEATING - Cont’d
LONG TERM OVERHEATING - Cont’d Complete spheroidization of iron carbides

Complete spheroidization of iron carbides

LONG TERM OVERHEATING - Cont’d
LONG TERM OVERHEATING - Cont’d
LONG TERM OVERHEATING - Cont’d Graphitization

Graphitization

LONG TERM OVERHEATING - Cont’d
LONG TERM OVERHEATING - Cont’d

Creep Voids

LONG TERM OVERHEATING - Cont’d
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: Where: P = T (20 + Log t) P =

OVERHEATING – Cont’d

OVERHEATING – Cont’d Larson-Miller Parameter: Where: P = T (20 + Log t) P = Larson-Miller

Larson-Miller Parameter:

Where:

P = T (20 + Log t)

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

HYDROGEN DAMAGE

HYDROGEN DAMAGE • Typically occurs: – Waterwall tubes above operating 1000 psig – Beneath heavy deposits

Typically occurs:

Waterwall tubes above operating 1000 psig Beneath heavy deposits

Where corrosion releases atomic hydrogen

HYDROGEN DAMAGE – Cont’d
HYDROGEN DAMAGE – Cont’d
HYDROGEN DAMAGE – Cont’d Concentrated Sodium Hydroxide Mechanism: 4NaOH + Fe 3 O 4 → 2NaFeO

Concentrated Sodium Hydroxide Mechanism:

4NaOH + Fe 3 O 4 2NaFeO 2 + Na 2 FeO 2 + 2H 2 O

Fe + 2NaOH Na 2 FeO 2 + 2H

4H +

+ Fe 3 C

CH 4

+ 3Fe

HYDROGEN DAMAGE – Cont’d
HYDROGEN DAMAGE – Cont’d

Thick-lipped

Brittle appearance

Window sections (sometimes) blown out

HYDROGEN DAMAGE – Cont’d
HYDROGEN DAMAGE – Cont’d
HYDROGEN DAMAGE – Cont’d Microstructure exhibits: – Short discontinuous intergranular cracks – Decarburization

Microstructure exhibits:

Short discontinuous intergranular cracks

Decarburization

CAUSTIC GOUGING
CAUSTIC GOUGING
CAUSTIC GOUGING • Caustic concentrates - DNB or steam blanketing • NaOH beneath deposits destroys protective
CAUSTIC GOUGING • Caustic concentrates - DNB or steam blanketing • NaOH beneath deposits destroys protective

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
OXYGEN ATTACK
OXYGEN ATTACK • Dissolved O 2 yields cathodic depolarization • Reddish-brown hematite (Fe 2 O 3
OXYGEN ATTACK • Dissolved O 2 yields cathodic depolarization • Reddish-brown hematite (Fe 2 O 3

Dissolved O 2 yields cathodic depolarization

Reddish-brown hematite (Fe 2 O 3 ) or “rust” deposits or tubercles

Hemispherical pitting beneath deposits

THERMAL FATIGUE
THERMAL FATIGUE
THERMAL FATIGUE • Numerous cracks and crazing, oxide wedge • Caused by: – Excessive cyclic thermal
THERMAL FATIGUE • Numerous cracks and crazing, oxide wedge • Caused by: – Excessive cyclic thermal

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
FLOW ASSISTED CORROSION
FLOW ASSISTED CORROSION • Localized thinning • Dissolution of protective oxide and base metal • Occurs

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
FLOW ASSISTED CORROSION – Cont’d
FLOW ASSISTED CORROSION – Cont’d • FAC affected by: – Temperature – pH – O 2

FAC affected by:

Temperature

pH

O 2 concentration

Mass flow rate

Geometry

Quality of fluid

Alloys of construction

FLOW ASSISTED CORROSION – Cont’d 1.2 1.0 0.8 0.6 0.4 0.2 0.0 Noralized Wear Rate

FLOW ASSISTED CORROSION – Cont’d

1.2 1.0 0.8 0.6 0.4 0.2 0.0 Noralized Wear Rate
1.2
1.0
0.8
0.6
0.4
0.2
0.0
Noralized Wear Rate

100 150 200 250 300 350 400 450 500 550

Temperature ( 0 F)

Greatest potential for FAC occurs around 300 ºF

Normalized Wear Rate

FLOW ASSISTED CORROSION – Cont’d
FLOW ASSISTED CORROSION – Cont’d

40

30

20

10

0

8.6 8.8 9.0 9.2 9.4
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
FLOW ASSISTED CORROSION – Cont’d
35 30 25 20 15 10 5 0 0 10 20 30 40 50 60
35
30
25
20
15
10
5
0
0 10
20
30
40
50
60
70
80
90 100
Noralized Wear Rate

Oxygen Concentration (ppb)

Dissolved oxygen has direct impact

FAC minimized above 30 ppb O 2

FAC increases exponentially below 30 ppb O 2

FLOW ASSISTED CORROSION – Cont’d
FLOW ASSISTED CORROSION – Cont’d
2.8 2.6 2.4 2.0 1.8 1.6 1.4 1.2 1.0 10 20 30 40 50 60
2.8
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
Noralized Wear Rate

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
FLOW ASSISTED CORROSION – Cont’d

Wear at

Wear due to Secondary Flow at

Low Re

Medium Re

Numbers

Numbers

Wear at
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

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:
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 East Economizer side 5 10 15 20 25 30 35 40

Map of Tube Failures

East

Economizer side

5 10 15 20 25 30 35 40 45 50 55
5
10
15
20
25
30
35
40
45
50
55

FailedFailures East Economizer side 5 10 15 20 25 30 35 40 45 50 55 Scale

Scale detectedMap of Tube Failures East Economizer side 5 10 15 20 25 30 35 40 45

Borescoped - CleanMap of Tube Failures East Economizer side 5 10 15 20 25 30 35 40 45

Fire Box Side

Operating Conditions-Video Probe View
Operating Conditions-Video Probe View
Notice iron oxide film has been compromised
Notice iron oxide film
has been compromised
Operating Conditions- Visual Inspection Notice layered iron oxide chips

Operating Conditions- Visual Inspection

Notice layered iron oxide chips
Notice layered iron oxide chips
As-Received for Laboratory Examination
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.

a complete wall failure at the external radius of the bend. Bottom/left photo illustrates the tube’s
a complete wall failure at the external radius of the bend. Bottom/left photo illustrates the tube’s

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

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
Through-wall gouging
ID (waterside) surface after cleaning. Note severe, localized gouging beneath deposits. Copper corrosion products also
ID (waterside) surface after cleaning. Note severe, localized
gouging beneath deposits. Copper corrosion products also

observed near gouged areas.

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.
Close up view of copper corrosion products observed near
gouged area of smooth finned tube.
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 copper corrosion products dispersed
throughout iron oxide matrix at ID surface.
Photomicrograph of copper corrosion products dispersed throughout iron oxide matrix at ID surface.
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
Photomicrograph of tube metal microstructure at gouged area.
Microstructure consists of normal lamellar pearlite and ferrite.

Nital Etch

Magnification 855 X

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

ID (waterside) surface of serrated-fin tube with localized accumulation of adherent, scab-like, rusty brown corrosion products.

Note waterline marks
Note waterline marks
Chemical Analysis of water soluble components from the iron oxide deposit at base metal interface
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
ID (waterside) surfaces of adjacent unfailed tubes exhibited thin,
non-magnetic, reddish deposit layer. DWD measured 5.2 g/ft 2 .
Remaining tubes were essentially free of corrosion and in excellent

condition.

deposit layer. DWD measured 5.2 g/ft 2 . Remaining tubes were essentially free of corrosion and
Failure Mechanism
Failure Mechanism
Thermal excesses and/or inadequate flow led to DNB/steam blanketing .
Thermal excesses and/or
inadequate flow led to
DNB/steam blanketing .
Failure Mechanism
Failure Mechanism
Failure Mechanism
Failure Mechanism
Thermal excesses and/or inadequate flow led to DNB/steam blanketing . •Scab-like deposits formed. •Anions
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-
Failure Mechanism-

Failed Tube Orientation

Failure Mechanism- Failed Tube Orientation
Failure Mechanism- Failed Tube Orientation
Failure Mechanism-
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

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 SO 4 anions

Maximum allowable stress is exceeded due to thinning

Corrective Actions &
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
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
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
Corrective Actions & Recommendations

Monitor BFW Quality

Install Online Analyzers

Cation Conductivity pH

Corrective Actions & Recommendations
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:
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 PO 4 and amines

Periodic upsets in O 2 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)
Cleaned Tubes (As Received)
Cleaned Tubes (As Received) • Localized pitting • Shallow corrosion • Maximum penetration (0.031”) 36% wall

Localized pitting

Shallow corrosion

Maximum penetration (0.031”) 36% wall loss

Undercut pitting suggests an acid form of attack

Cleaned Tubes (As Received)
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)
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/ft 2

Uncleaned Tubes (SEM-EDS)
Uncleaned Tubes (SEM-EDS)
Uncleaned Tubes (SEM-EDS) Iron 78.8% Iron 69.6% Oxygen 18.7% Oxygen 13.8% Sulfur 0.74%
Uncleaned Tubes (SEM-EDS) Iron 78.8% Iron 69.6% Oxygen 18.7% Oxygen 13.8% Sulfur 0.74%

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)
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)
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 • H 2 SO 4

Root Cause(s):

Root Cause(s): • Alloy substitution of plug in upstream unit • H 2 SO 4 “Black

Alloy substitution of plug in upstream unit

H 2 SO 4 “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

Corrective Actions:

Corrective Actions: • Water no longer considered a utility, but rather a part of the process

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
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:
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
Laboratory Examination:
Visual Inspection
Laboratory Examination: Visual Inspection • Thick adherent oxide on hot side • Severe gouging • Trace

Thick adherent oxide on hot side

Severe gouging

Trace white deposits at oxide tube interface

No maricite layer

oxide on hot side • Severe gouging • Trace white deposits at oxide tube interface •
oxide on hot side • Severe gouging • Trace white deposits at oxide tube interface •

Cracking

Laboratory Examination: Visual Inspection
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%
Laboratory Examination:
SEM-EDS
Phosphorus
20.1%
Manganese
18.3%

Analysis of deposits at oxide-metal interface

Sodium

16.0%

Iron

11.6%

Silicon

3.5%

Aluminum

1.0%

Calcium

0.3%

Oxygen

29.0%

Laboratory Examination: Microstructure
Laboratory Examination:
Microstructure
Laboratory Examination: Microstructure • Preferential attack at weld seam • Weld not normalized • In-situ

Preferential attack at weld seam

Weld not normalized

In-situ spheroidization

No decarburization observed

Preferential attack at weld seam • Weld not normalized • In-situ spheroidization • No decarburization observed
Laboratory Examination: Microstructure
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

Intergranular cracking at gouged area • Hydrogen induced crack at ERW seam • Characteristic of SCC
Laboratory Examination: Microstructure
Laboratory Examination:
Microstructure
Laboratory Examination: Microstructure • Numerous intergranular cracks at gouged area • Cracking is typical of

Numerous intergranular cracks at gouged area

Cracking is typical of hydrogen damage

Slight in-situ spheroidization around entire circumference

at gouged area • Cracking is typical of hydrogen damage • Slight in-situ spheroidization around entire
Laboratory Examination: Microstructure – (Separate tube)
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

Laboratory Examination:

Key Observations

Severe gouging along hot side of tube

Heavy magnetite deposit (corrosion product)

Distinct maricite (NaFePO 4 ) layer not observed

No evidence of Cl or SO 4 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

Laboratory Examination:

Follow-up Tube Analysis

Hot Side
Hot Side
Back Side
Back Side

Adjacent tube received one month later

Distinct waterline marking along hot side

Reddish-black friable deposits

Internal DWD (g/ft 2 ): 13.1 hot side, 9.1 back side

Laboratory Examination:
Laboratory Examination:

Follow-up Tube Analysis (Cont’d)

Laboratory Examination: Follow-up Tube Analysis (Cont’d) Iron 83.6% Manganese 1.3% Aluminum 0.5%

Iron

83.6%

Manganese

1.3%

Aluminum

0.5%

Phosphorus

0.4%

Calcium

0.3%

Oxygen

14.0%

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

Laboratory Examination: Follow-up Tube Analysis (Cont’d) Hot Side Adjacent Tube: Cold Side Internal appearance
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)
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

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
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.

and non-protective oxides will enhance wick boiling and under deposit forms of attack, especially in high
CASE HISTORY #3
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
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
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

©2006, Ashland