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Failure Analysis S

urface condensers are shell and


tube heat exchangers utilized to
convert exhaust steam from steam
turbines to steam condensate at a
pressure below atmospheric (Figure 1).

of Condenser The condensate may be reused in the


boiler as boiler feedwater.1-2
This article describes the ndings of a
detailed investigation of tube cracking in
two ethylene surface condensers that will

Tubes be referred to as E-1 and E-2. The main


objective of the study was to identify the
cause(s) of the failures and suggest correc-
tive action(s) to improve the plant reli-
AbdulAziz Al-MeshAri, SABIC Technology Centre, Jubail, Saudi Arabia ability. The condensers have been in
service for 25 years. In the condensers,
steam condensate ows into the shell side
and cooling water is introduced in the
Tis article describes a detailed investigation of tube side. The tube material in both
condensers is inhibited admiralty brass.

ethylene surface condenser tubes that cracked. Investigation


Four tube samples from condensers
Analyses attributed the condenser tube failures to E-1 and E-2 were examined. Multiple
transverse cracks were observed on the
stress corrosion cracking. Recommendations to samples, indicating that the cracking was
induced by bending stresses rather than
circumvent the tube cracking problem are provided. hoop stresses (Figure 2). Some of the
cracks appear to have propagated longi-
tudinally at the crack ends. Visual ex-
Upgrading of the tube metallurgy is also discussed. amination of the samples revealed no
signicant corrosion or tube thinning.
Also, examination of the tubes internal
surfaces showed no signs of degradation.

Material Evaluation
The tube material chemical composi-
tion was veried, and it conforms to the
chemical composition requirements for
inhibited admiralty brass stated in ASTM
B43-09.3 Inhibited admiralty brasses are
copper-zinc alloys noted for their im-
proved corrosion resistance to low-velocity
freshwater and seawater, and hence are
selected for condenser and heat exchanger
tubing in these environments.4
62 MATERIALS PERFORMANCE December 2012 NACE International, Vol. 51, No. 12
M AT E R I A L S S E L E C T I O N & D E S I G N

FIguRE 1

Metallographic Examination
Cross sections of the tube samples
were prepared for metallographic ex-
amination (Figure 3). The tubes outside
diameter (OD) surfaces were covered
with a continuous layer (tarnish lm),
typically 10 m thick. Obviously, the
cracks had started locally from the tubes Diagram of a typical water-cooled surface condenser.
OD at oxides-attributed sites and propa-
gated intergranularly (Figure 4). More- FIguRE 2
over, the cracks were completely lled
with oxides. The presence of multiple
cracks running near each other at the
cracking region may suggest that the ap-
plied stress had been relatively low. Inter-
estingly, localized dealloying (plug de
zincication) was found at the tubes OD
surfaces.
Scanning electron microscope/energy
dispersive x-ray (SEM/EDX) analysis Transverse cracks observed on the condenser tube samples.
showed that the products formed inside
the cracks were composed mainly of cop- FIguRE 3
per oxides (Figure 5). Traces of Mg, Al,
Si, Ca, Cr, Mn, C, Cl, Na, and Ni were
also detected inside the cracks. It is also
worth noting that considerable iron con-
centration was found in the layer formed
on the tubes OD surfaces.

Water Analysis
Steam condensate samples from both
condensers were collected and analyzed.
The pH of the condensate varied from
7.5 to 8.5. The water analysis also
conrmed the presence of ammonium
(the maximum concentration detected
was 0.2 ppm). Chloride was also found
(~0.8 ppm).

Results
These ndings clearly indicate that the
condenser tube failures were caused by
ammonia (NH3) stress corrosion cracking
(SCC). Indeed, brasses containing 20 to
40% Zn (admiralty brass) are highly sus- Intergranular cracks and localized dezincication on the tube cross sections.
ceptible to SCC that can be induced by Note the oxides formation in the cracks. As polished.

NACE International, Vol. 51, No. 12 December 2012 MATERIALS PERFORMANCE 63


M AT E R I A L S S E L E C T I O N & D E S I G N Failure Analysis of Condenser Tubes

FIguRE 1

the environment is necessary for SCC to


take place. Carbon dioxide (CO2) is also
thought to accelerate SCC.8-9 Dezincica-
tion usually occurs in copper zinc alloys
containing <85% copper when they are
in contact with water having high oxygen
or CO2 content or in stagnant solutions.6
It has been suggested that the tarnish
lm copper (1) oxide (Cu2O) forming and
growing on the tube surface tends to
grow through the grain boundaries.
Therefore, the presence of a tarnish lm
can be used as an indication of inter-
granular SCC. SCC occurs from re-
peated cracking of the grain boundary
oxides (by applied stresses) and exposure
Crack morphology revealed by etching. of fresh grain boundary at the depth of
the crack that, in turn, corrodes by the
FIguRE 2 environment. This is followed by further
formation of oxides, which then crack at
a critical increment of penetration.5,7 The
corrosion reactions taking place on brass
surfaces may be expressed as the follow-
ing equations:7

Anodic reaction: (1)


Cu + nNH3 + O2 + H2O
Cu(NH3)n2+ + 2OH

Cathodic reaction: (2)


Cu(NH3)52+ + e Cu(NH3)2+ + 3NH3

Precipitation reaction: (3)


2Cu(NH3)2+ + 2OH Cu2O + 2NH3 + H2O

It has been reported that the optimum


pH range and maximum NH3 concentra-
tion for the steam systems containing
admiralty brass condenser tubes is 8.8-9.1
and 0.5 ppm respectively. This concen-
SEM/EDX analysis of the deposit found on the tube surface and inside the crack tration can be deemed too high if air
(wt%). leakage occurs.9

small amounts of NH3.5 It has been docu- addition, NH 3 and ammonium com- Conclusion
mented that very small concentrations of pounds are sometimes used as constitu- The failure analysis concluded that the
NH3 (1 ppm or less) can lead to SCC in ents of the steam treatment program. condenser tube cracks were caused by
copper and copper alloys.6 Ammonium NH3 dissolves in the water lm that forms NH3 SCC.
can be produced when nitrogen oxides on the tubes and produces concentrations
react with brass surfaces. Nitrogen oxides signicantly higher than those of the bulk Recommendations
may be introduced into the condenser water. It is also well recognized that the The steam condensate pH, ammo-
due to leaking of air into the system.7 In presence of an oxidizer such as oxygen in nium, and dissolved oxygen levels in
64 MATERIALS PERFORMANCE December 2012 NACE International, Vol. 51, No. 12
M AT E R I A L S S E L E C T I O N & D E S I G N

the system should be monitored, 4 Copper Development Association,


adjusted, and constantly kept within http://www.copperinfo.co.uk
(Oct. 23, 2012).
the design limits.
5 L.J. Korb, ASM Metals Handbook, Vol. 13,
The water treatment program used Corrosion (Materials Park, OH: ASM
in the system should be reviewed for International, 1992).
NH3 and/or NH3-producing com- 6 M.P. Schwartz, Four Types of Heat
pounds. If the water treatment Exchanger Failures, Plant Engineering,
program contains these compounds, 1982.
then an NH3-free water treatment 7 B.F. Brown, Stress Corrosion Cracking
program should be applied. Control Plans, 3. Copper Alloys, NTIS,
AD-A012 872, 1975.
The system should be checked for
8 L. Caruso, H.T. Michles, The
air leakage. Air leakage into the Resistance of Copper-Nickel Alloys to
system may lead to increases in oxy- Ammonia Corrosion in Simulated Steam
gen, CO2, and ammonium levels, Condenser Environments, Proc.
American Power Conference (Chicago,
and higher probability of SCC.
IL: Illinois Institute of Technology,
If the levels of oxygen and other 1980).
contaminants cannot be controlled 9 B. Buecker, Control Water Chemistry
using these recommendations, then in Heat Recovery Steam Generators,
upgrading metallurgy of the tubes Chemical Engineering Progress, 2000.
may be considered, such as replac- 10 90/10 Copper-Nickel vs. Sea-Cure
ing the existing inhibited admiralty Stainless Steel, A Functional Compari-
son of Two Condenser Tube Alloys,
brass tubes with 90/10 copper- Olin Brass Fineweld Tube, Technical
nickel tubes. This alloy exhibits Letter.
good resistance to SCC as well as
general corrosion, but has poor ABDULAZIZ AL-MESHARI is a staff scientist at SABIC
Technology Centre, PO Box 11669, Jubail Industrial
resistance to sulde-induced pitting. City, 31961, Saudi Arabia, e-mail: meshariai@
Indeed, it has been reported in lit- sabic.com. He is a failure analysis expert with more
erature that a 90/10 copper-nickel than 14 years of experience and has published
several papers on corrosion, failure analyses, and
alloy cannot be used in cooling related topics. He has an M.Sc. degree from UMIST
waters containing >10 ppm sul- and a Ph.D. from the University of Cambridge. He
fides.10 It should also be kept in has been a member of NACE International since
2000.
mind that an NH 3-free water
treatment program should be ad-
opted even if a decision is made to
upgrade the tube material to 90/10
nickel-copper.
NACE International offers
References more than 400 books
1 Steam: Its Generation and Use, 41st ed. covering every aspect
(Charlotte, NC: Babcock & Wilcox Co., of corrosion control in
2005).
all industries. For more
2 R.E. Putnam, Steam Surface Condensers:
Basic Principles, Performance, Monitoring and information, visit the
Maintenance (New York, NY: ASME
NACE Store at
Press, 2001).
www.nace.org.
3 ASTM B43-09, Standard Specication
for Seamless Red Brass Pipe, Standard
Sizes (West Conshohocken, PA:
ASTM).

NACE International, Vol. 51, No. 12 December 2012 MATERIALS PERFORMANCE 65

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