NACE CENTRAL AREA

CONFERENCE 2006
Wednesday, October 4
Waterside Corrosion Session
A Failure Analysis Investigation of
Pitting in Type 316L Piping
Bearing Seawater Used for Cooling

Presented by Paul Redmond

Southwest Research Institute®
NACE Central Area Conference 2006 1
 Acknowledgments
This presentation summarized work
performed by Dr. Narasi Sridhar, Dr. Sean
Brassia, and Darrell Dunn.
Acknowledgments are also extended to
Melissa Hill, Harold Saldana, Fawn Daby,
and other members of the Materials
Applications staff.

NACE Central Area Conference 2006 2

 OUTLINE
1. About the Southwest Research Insitute
2. Background of Type 316L SS installation
and startup issues
3. Timeline
4. Mitigating Issues
5. Startup
6. Analysis of pipe segments
NACE Central Area Conference 2006 3
 OUTLINE (CONT.)
5. Biological Subcultures
6. Laboratory Simulations
7. Literature Review
8. Summary
9. Recommendations
10. References

NACE Central Area Conference 2006 4

 Facts About
Southwest Research Institute®
• 59 years of operation
• 501 (c)(3) nonprofit corporation
• 3,000 employees
• 1,200 acre facility in San Antonio, TX
• >2 million ft2 of laboratories & offices
• Over 700 patents
• 28 R&D 100 awards
NACE Central Area Conference 2006 5
 ®
SwRI Mission and Purpose
• Founded in 1947 by
Thomas Baker Slick Jr.
• Charter
– Nonprofit organization
– Independent &
unbiased
– Betterment of mankind
through science and
technology
– Development &
transfer of technology
NACE Central Area Conference 2006 6
 ®
SwRI Today

NACE Central Area Conference 2006 7

 Operating Research Divisions
at SwRI
• Chemistry & Chemical Engineering
• Engine, Emissions and Vehicle Research
• Training, Simulation and Performance Improvement
• Fuels and Lubricants Research
• Aerospace Electronics and Information Technology
• Automation & Data Systems
• Applied Physics
• Space Science and Engineering
• Signal Exploitation and Geolocation
• Mechanical & Materials Engineering
• Center for Nuclear Waste Regulatory Analyses
NACE Central Area Conference 2006 8
 My Operating Division
Approximately 235 personnel
Mechanical and Materials
Engineering Division

Engineering Materials Mechanical and Structural

Dynamics Engineering Fluids Engineering Engineering
computational mechanical plant engineering aerospace
mechanics testing structures
multiphase flow
ballistics and reliability and structural
mechanical sciences
explosives materials systems
piping
surface testing/evaluation
design/analysis
engineering
flow measurement
material
applications rotating machinery
NACE Central Area Conference 2006 9
 Background

• Gas fired cogeneration plant in Puerto Rico.

• A combination of Type 316L piping and

Fiberglass Reinforced Plastic (FRP) piping
at pier level.

• High Density Polyethylene (HDPE) piping

installed in certain underground locations.

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 Background

• Seawater pumps were made of Type 317L.

• Cathodic protection of Type 317L.

• Protection of pumps exterior only.

• Condenser tubing and plate heat exchangers

composed of titanium.

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 Timeline for the Cooling System
Taken from the Plant Logs
System Activity March April May June July August September October November Dec. Jan,2000 Feb.
Seawater Supply-Lines filled w/ Peerless water ?
-Hydrotest 15 20 2 10
-Lines filled w/ seawater 7
-In service 12 3
-Out of service 21
Seawater Make--Lines filled w/Peerless water ?
-Hydrotest 15 20 2 10
-Lines filled w/ seawater 7
-In service 11
-Out of service 21
-Biological growth evident 23
-Start system, found several pinhole leaks

- Filled with Peerless potable water

- Stagnant
- Intermittent Flow
- In service

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 Time Line Details
• Hydrotesting with well water.

• During repeated hydrotests stagnant well water

was left in the system for up to 3 months.

• No chlorination for the first 4 months.

• Well water was gradually pushed out by seawater

and left stagnant for at least 1 week.

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 Time Line Details (cont.)

• Intermittent trial operations; stagnant seawater

left in the system for up to 2 weeks.

• Could not drain the system due to concerns of

collapsing FRP lines from vacuum.

• Inspection of the system found an inadequate

number of drain points.
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 Mitigating Issues
Chlorination
The absence of chlorination in the system during
the first 4 months due to:

– Environmental permit restrictions of

0.5 ppm max and 0.2 ppm avg daily.

– Key chlorination pump was out of service.

– Initial chlorination injection was only in the

cooling tower.

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 After Startup
• Pitting leaks were detected in many Type 316L
piping locations within 2 weeks ( > 375 mils).

• Leaks were predominantly in seawater supply

lines, but later in return lines as well.

• Several patches/welds applied, but new leaks

continued to appear.

• No leaks were observed in FRP and HDPE lines.

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 Photograph of a
Leaking Seawater Supply Pipe

The two bands indicate areas clamped with

patches on the outside diameter.
NACE Central Area Conference 2006 17
 Analysis
A segment of failed Type 316 piping was sent
to Southwest Research Institute (SwRI ) for:

1. Root cause failure analysis;

2. Prognostications of future performance

of un-pitted sections (if possible).

NACE Central Area Conference 2006 18

 Metallographic Analysis
• No evidence of intrinsic material or
fabrication defects.

• No evidence of intergranular precipitates,

secondary cracks, etc.

• Shape and morphology of internal pitting

suggestive of MIC.
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 Overall View of a Pit from the
I.D. Surface and the Transverse
Cross-Section Across the Pit
I.D.

2 mm

1.3 mm O.D.

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 Energy Dispersive Spectroscopy
Analysis of Solids Collected
at the Mouth of Pits
Na Mg Al Si P S Cl K Ca Ti Cr Fe Ni
8.0 3.6 11.0 24.9 0.3 1.7 16.5 2.0 13.3 0.7 1.3 16.1 0.7

• High amounts of Si, Al (possibly from sand).

• Cl, Na, Mg, and K (from seawater).
• Ca (from barnacles?).
• S (possibly from sulfate reducing bacteria [SRB]).

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 X-Ray Diffraction
• X-ray diffraction of solids found indications
of NaCl and (gamma FeOOH).

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 Biological Subcultures
• Subcultures were generated from water and
pipe deposit samples.

• Barnacles within the deposits were

manually removed.

• Subcultures were incubated in Marine Broth

2216 under aerobic conditions.
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 Biological Subculture Results
• Marine Broth 2216 cultures tested positive
for slime.

• Thick mucoid colonies were successfully

subculture on agar in aerobic conditions.

• Possible third type of bacterium was

observed but unidentified.
NACE Central Area Conference 2006 24
 Biological Subculture Results (cont.)
• Deposits and water samples sub-cultured in Baar’s
Medium modified with 2.5% NaCl under anaerobic
conditions.
• Pipe deposits tested positive for SRBs

• Positive evidence of SRBs in slime.

• No initial evidence of SRBs in water cultures

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Laboratory Simulations

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 Pitting Testing of Type 316L in
Stagnant Seawater
• Pipe freshly polished to 600 grit; strung between Teflon
fasteners.

• Exposed to seawater collected at the plant in 200 ml flask

(roughly 20°C) for 26 days.

• Crevice corrosion was observed (up to 4 mils or 100 µm).

• No pitting was observed in non-crevice areas.

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 Open Circuit Potential Testing
• Sealed water collected from three locations:
– Inlet;
– After Heat Exchanger; and
– Return.
• Machined Type 316L and Alloy C-22 cylindrical
specimens.
• Solutions left open to ambient atmosphere; stirred to
mimic flow.
• Open circuit potential was constantly monitored.

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 Measured Open-Circuit Potential of
Type 316L Stainless in Three Locations
o
316L SS and Alloy C-22 Open Circuit Potentials, 25 C
0.05

0.00

C-22 Fresh Seawater

-0.05
Potential, VSCE

316L Fresh Seawater

-0.10
316L Heat Exchanger Inlet

C-22 Heat Exchanger Inlet

-0.15
316L Return Water

-0.20
C-22 Return Water

-0.25

-0.30
0 5 10 15 20 25 30 35 40

Time, h
NACE Central Area Conference 2006 29
 Observations
• Open circuit potential of type of Type 316L noticeable
higher in fresh seawater.
• At the inlet compared to after heat exchanger and return.
• Hastalloy C-22 exhibited the same behavior over time.

• Evolution of circuit potentials occurred over several days.

• Can be related to establishments of thin biofilms and

changes in oxide films (Dickenson, et al., 1986).

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 Observations (cont.)
• Protection potentials for Type 316L at 20°C in seawater
s/b in the range of 0 mV vs. SCE.

• Results suggest that after heat exchanger and return

piping would be less susceptible vs. inlet.

• Such single point measurements are useful for

comparison but not for life predictions.

• Protection potentials and open circuit potentials can have

a range of values in service.

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 Chlorine Measurements
1

0.9
Cl, tower
0.8
Cl, sea
0.7
Chlorine, ppm

0.6

0.5

0.4

0.3

0.2

0.1

0
99

99

99

99
9

9
/9

/9

/9

/9

/9

/9

/9

/9

/9

/9

/9

/9

/9
2/

8/
4/

6/
29

31

10

12

14

16

18

20

22

24

26

28

30
9/

9/

9/

9/

9/
8/

8/

9/
9/

9/

9/

9/

9/

9/
9/

9/

9/
Date

A sampling of chlorine analysis over a period of about

1 month, indicating relatively low residual chlorine levels.
NACE Central Area Conference 2006 32
 Chlorine Measurements (cont.)
• Noted at the plant during inspection that chlorine
monitors were not calibrated.

• Unknown error in measurements.

• Measurements made on seawater side and blowdown

to the helper cooling tower.

• Can be inferred that chlorine levels were lower

seawater side vs. near the cooling tower.

NACE Central Area Conference 2006 33

 Literature Review
• Infant pits nucleate underneath breached oxide films.

• Hydrolysis reactions:
– Fe2+ + 2H2O Fe(OH)2 + 2H+
– Cr3+ + 3H2O Fe(OH)3 + 3H+
– Ni2+ + 2H2O Ni(OH)2 + 2H+

• Minimal mixing of internal/external solutions and

compromised passivity.

• Crevice corrosion, oxygen depletion, lack of mixing

of pit solution with external solution.
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 Literature Review (cont.)
• Natural seawater has been noted to be more
aggressive than artificial.

• It has been shown that microbial organism can

increase the open circuit potential.

• A process called ennoblement (Motoda, et al., 1990;

Audouard, et al., 1995).
NACE Central Area Conference 2006 35
 Literature Review (cont.)
• SRB can also initiate localized attack.

• Generation of sulfides can reduce the

protection potential encouraging localized
attack.

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 Literature Review (cont.)
Kinetics of Localized Attack in Stagnant
Seawater Varied
• Shallow Water depths <5 ft.; depths up to 230 mils
(5.8 mm) after 181 days exposure (Schumacher,
1979).

• 25.4 mils (0.635 mm) pit depths in seawater

cooled lube oil heat exchangers after 3 months
(Shalaby and Husain, 1992).

NACE Central Area Conference 2006 37

 Literature Review (cont.)
Localized Attack in Flowing Seawater
• 76 mils (1.9 mm) within 30 days, in flowing
seawater (0.06 m/s) at 14°C (Asphahani, et al.,
1980).
• 20 mils in 100 days in 0.7 – 1.0 m/s (Shone et al
1988)
• Under flowing conditions, pitting becomes less
susceptible.
• However, crevice attack may still occur in flanged
joints, or under deposits or films (Lee and Tuthill,
1982; Shone, et al., 1988; Kain, 1998).
NACE Central Area Conference 2006 38
 Literature Review (cont.)
Temperature Effects in Seawater
• Severity of attack in seawater attains a maximum at
30°C.
• Above 30°C the open circuit potential drops due to
destabilization of biofilms (Steinsmo, et al., 1997;
Mullica et al 1989).
• Does not diminish with increasing temperatures in
chlorinated seawater (1.0 ppm).
– Residual chlorine sets up its own high redox potential
irrespective of biofilms (Steinsmo, et al., 1997)

NACE Central Area Conference 2006 39

 Literature Review (cont.)
Chlorination Effects in Seawater
• Chlorination successful in mitigating macrofouling of
surfaces (Goodman, 1987).

• Typical range is 0.2 ppm to 0.5 ppm for fresh water.

• Levels as low as 0.1 ppm, sufficient to kill microbial slime

layers on surfaces; minimum open circuit potential in
flowing seawater (Shone, et al., 1988).

• Residual chlorine can act as an oxidant and increasing

chances of localized attack.
– Steinsmo, et al., 1997 measure open circuit potentials about 600 mv vs. SCE
in 22%Cr duplex stainless steel in a 1 ppm chlorinated solution.

NACE Central Area Conference 2006 40

 Literature Review (cont.)
Cathodic Protection in Seawater
• If the opened circuit potential is depressed below the
protection potential localized attack will not continue.

• Cathodic protection (galvanic coupling to iron/carbon

steel, zinc, and/or impressed current) can protect stainless
steels against localized attack in seawater (Lennox, et al.,
1983; Baptista and Pimenta, 1995; Valen, et al., 1999;
Sedriks, 1982).

• Incidental protection by coupling carbon steel (Lee and

Tuthill, 1982).

NACE Central Area Conference 2006 41

 Literature Review (cont.)
Localized Attack in Fresh Water

• Localized attack; rare but has been documented.

• Kovach (1999) documented five cases of pitting in Type 316L piping

possibly due to high Mn and chlorination -> formation of
permanganeate.

• Dickenson, et al., (1996) found evidence of biofilm induced

ennoblement of Type 316L in flowing freshwater.

• Numerous examples of pitting of Type 316L with residual well water

being left in piping after hydrotesting (Kobrin [1986] as typical).

NACE Central Area Conference 2006 42

 Summary
• Through wall pitting in a short period of time (375 mils
in 6 weeks) was more severe than normally observed
even in stagnant water conditions.

• Appeared to be almost instantaneous.

• Such pitting rates were not observed in comparable

laboratory experiments.

• Not attributable to metallurgical factors.

NACE Central Area Conference 2006 43

 Summary (cont.)
• Stagnant water conditions (well water)
were created during prolonged hydrotesting
(leak free joints could not be attained).

• Proper draining was not attempted to avoid

collapsing fiber reinforced piping (FRP).

• Early plant operations were intermittent

prolonging stagnant seawater conditions.
NACE Central Area Conference 2006 44
 Summary (cont.)
• Excess Chlorine levels (0.5 to 0.8 ppm) could cause
premature pitting; however:
– Environmental restrictions on chlorine discharge;
– Lack of calibrated monitoring; and
– Early chlorine pump failure.

• Actual chlorine levels likely seldom exceeded

0.2 ppm.

• Absence of sufficient chlorination during hydrotesting/

intermittent operations, lead to the establishment of an
active microbial consortium of biofilm formers and
SRBs.
NACE Central Area Conference 2006 45
 Summary (cont.)
• SRBs can reduce the protective potential.
• The presence of marine microorganisms can raise the
open circuit potential.
• The two factors combine likely lead to the apparent
instantaneous local attack.
• Once established even rapid flowing seawater would
be insufficient to stop localized attack.

• Weld/patches over existing leaks can exacerbate

existing pitting leading to crevice corrosion.
NACE Central Area Conference 2006 46
 Summary (cont.)
• Type 317L seawater pumps were CP protected
on exteriors only.

• Current flow spill over into interior components

could not be addressed.

• Anode placement possibly problematic with

insufficient protection of interior components.
NACE Central Area Conference 2006 47
 Recommendations
1. Most Type 316L segments should be replaced with
FRP.

2. Remaining Type 316L segments can be used to

provide:
a. Cathodic Protection (CP); and
b. Proper continuous through system chlorination (0.2 ppm)
is maintained.

3. Careful monitoring of the Type 317L pumps.

Reallocation of anodes S/B considered.

NACE Central Area Conference 2006 48

 Recommendations (cont.)
4. Corrosion monitoring of remaining Type 316L
segments:
a. Potential measurements (reference electrodes); and
b. Measuring dissolved iron not useful due to dilution.

5. Increase the number of drain points in FRP.

6. Rewrite plant startup and operation procedures to

reflect lessons learned.
NACE Central Area Conference 2006 49
 References
• Asphahani, A.I., P.E. Manning, W.L. Silence, and F.G. Hodge. 1989. Highly
Alloyed Stainless Materials for Seawater Applications. Kokomo, IN: Haynes
International.
• Auduard, J.P., C. Compere, N.J.E. Dowling, D. Feron, D. Festy, A. Mollica, T.
Rogne, V. Scotto, U. Steinsmo, C. Taxen, and D. Thierry, 1995. Effect of
marine biofilms on stainless steels – results from a European exposure
program. Paper No. 3, 1995 International Conference on Microbially
Influenced Corrosion. Houston, TX: NACE International.
• Baptista, W. and G. Pimenta. 1995. Cathodic protection against crevice
corrosion of high-alloy steel in seawater. Materials Performance. V.34. pp.
29-32.
• Dickinson, W.H., Z. Lewandowski, and R.D. Greer, 1996. Evidence of surface
changes during ennoblement of type 316L stainless steel: dissolved oxidant
and capacitance measurements. Corrosion. V.52. pp. 910-920.
• Kobrin, G., 1986. Reflections on microbially influenced corrosion of stainless
steels, Biologically Induced Corrosion, S.C. Dexter (ed.), Houston, TX: NACE
International. pp. 33-46.

NACE Central Area Conference 2006 50

 References (Cont.)
• Kovach, C.W., 1999. Types 304 and 316 stainless steels can experience
permanganate pitting in water-handling systems. Materials Performance.
V.38. pp. 70-75.
• Lee, T.S. and A.H. Tuthill. 1982. Guidelines for the use of carbon steel to
mitigate crevice corrosion of stainless steel in seawater. Corrosion/82. Paper
No. 63. Houston, TX: NACE International.
• Lennox, T.J., M.H. Peterson, and C.W. Billow. 1983. Corrosion resistance and
response to cathodic protection of advanced alloys in seawater. Materials
Performance. V.22. pp. 49-55.
• Mollica, A., A. Travis, E. Traverso, G. Ventura, G. de Garolis, and R.
Dellepiane. 1989. Cathodic performance of stainless steels in natural seawater
as a function of microorganism settlement and temperature. Corrosion. V.45.
pp. 48-56.
• Motoda, S., Y. Suzuki, T. Shinohara, and S. Tsujikawa. 1990. The effect of
marine fouling on the ennoblement of electrode potential for stainless steels.
Corrosion Science. V.31. pp. 515-520.

NACE Central Area Conference 2006 51

 References (Cont.)
• Schumacher, M. 1979. Seawater Corrosion Handbook. Park Ridge,
NJ: Noyes Data Corporation.
• Sedriks, A.J. 1982. Corrosion resistance of austenitic Fe-Cr-Ni-Mo
alloys in marine environments. International Metals Reviews. V.27.
pp.321-353.
• Shalaby, H.M. and A. Husain. 1992. Localized corrosion of electric
resistance welds of austenitic stainless steel in seawater. British
Corrosion Journal. V.27. pp. 45-49.
• Shone, E.B., R.E. Malpas, and P. Gallagher. 1988. Stainless Steels As
Replacement Materials For Copper Alloys In Seawater Handling
Systems. Institute of Marine Engineers Presentation.
• Steinsmo, U., T. Rogne, and J. Drugli. 1997. Aspects of testing and
selecting stainless steels for seawater applications. Corrosion. V.53.
pp. 955-964.

NACE Central Area Conference 2006 52

 References (Cont.)
• Strandmyr, O. and D. Hagerup, 1998. Field experience
with stainless steel materials in seawater systems,
Corrosion/98, Paper No. 707, Houston, TX, NACE
International.
• Streicher, M.A. 1983. Analysis of crevice corrosion data
from two seawater exposure tests on stainless alloys.
Materials Performance. V.22. pp. 37-50.
• Valen, S., R. Johnsen, P.O. Gartland, and J.M. Drugli.
1999. Seawater piping systems designed with AISI 316
and RCP anodes. Corrosion/99. Paper No. 321. Houston,
TX: NACE International.

NACE Central Area Conference 2006 53