BOILER AND HRSG TUBE FAILURES

PPChem 1 1 0 01 1
LESSON 4:
Hydrogen Damage
R. Barry Dooley and Albert Bursik
PPChem 101 Boiler and HRSG Tube Failures
122 PowerPlant Chemistry 2010, 12(2)
INTRODUCTION
In Lesson 3 of this course Underdeposit Corrosion A
General Introduction presented in the December 2009
issue of the PowerPlant Chemistry journal, a general
review of features common to all underdeposit corrosion
mechanisms relevant to boiler and HRSG tubes was intro-
duced. In this lesson, the focus is on hydrogen damage,
which is the most frequently occurring underdeposit cor-
rosion mechanism.
LOCATIONS OF FAILURES FOR FOSSIL PLANTS
AND HRSGS
Hydrogen damage a special type of underdeposit corro-
sion may develop solely in locations where excessive
deposits, mostly of feedwater corrosion products, are
formed. The corrosion products typically originate in the
pre-boiler part of the cycle. They are generated in conden-
sate and feedwater touched cycle components and trans-
ported with the feedwater into the boiler. Single-phase
and two-phase flow-accelerated corrosion of cycle com-
ponents is the major source of the corrosion products
introduced in the boiler or heat recovery steam generator.
The transport of iron oxides (magnetite or hematite)
depends on the feedwater treatment applied. If copper
alloys are employed in the feedwater system then copper
oxides will transport into the boiler leaving pure copper
within the deposits.
The locations where underdeposit corrosion occurs are
those where excessive deposits form. Endangered are all
locations where the water flow adjacent to the tube wall is
disrupted in some way. There are many possible reasons
for the flow to become disrupted. In conventional plants,
the most susceptible locations are:
locations with existing internal deposits caused by
locally high heat flux
locally high steam quality
other deposition mechanisms
geometrical flow disrupters such as
improper welds
backing rings
poorly executed weld overlays and pad welds which
penetrate the tube wall to the inside surface
existing internal deposits
bends around burners or openings
tubes which are not vertical and are heated from
above or below such as nose or arch tubes
sharp changes of directions
tubes bending off lower headers and drums
localized overheating due to inadequate fireside condi-
tions
local overheating of the tube due to fireside flame
impingement
local overheating of the tube due to burner misalign-
ment
localized overheating due to operating conditions
local overheating as result of fuel changes
overfiring or gas channeling
local high steam quality
thermal-hydraulic disrupters as
locations with local very high steam quality
locations with horizontal or inclined tubes
Figures 13 show some geometrical flow disruptors
related to incorrect weld repairs.
In HRSGs, deposition and hydrogen damage occur on
both horizontal and vertical high pressure (HP) evaporator
tubing. On vertical tubing, the deposition concentrates on
the inner tube side crown of the tube facing the gas tur-
bine (GT). It nearly always is heaviest on the leading HP
evaporator tube in the circuit as these have the areas of
maximum heat transfer. The hydrogen damage mecha -
nism occurs in exactly the same areas. Tubes adjacent to
a side wall or the gap between side-by-side modules are
especially at risk. Exhaust gas bypassing results in greater
heat transfer there. On horizontal tubing both deposition
and the hydrogen damage mechanism occur on the inner
tube side crown facing towards or away from the gas tur-
bine. Damage usually occurs on the side facing away from
the GT when poor circulation rates, steaming or steam
2010 by Waesseri GmbH. All rights reserved.
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PPChem 101 Boiler and HRSG Tube Failures
123 PowerPlant Chemistry 2010, 12(2)
blanketing occur. These can lead to stratification of water
and steam and subsequent heavy deposition in a band
along the top of the tubing.
In these locations, in the presence of excessive deposits,
possible acidic boiler water contaminants (for example
chlorides or sulfates) may concentrate up to dangerous
levels.
Figure 1:
Tube inner surface showing heavy local deposits from
penetration of weld repair to the tube inside.
Figure 2:
Roof tube with pad
weld showing pene -
tration through to the
tube inside. This pene -
tration acts as a flow
disruption.
Figure 3:
Weld repair showing through to the tube inside
becomes a flow disruption.
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TYPICAL CHARACTERISTICS OF DAMAGE IN
BOTH PLANTS
The most important features of hydrogen damage are
summarized in Table 1.
Mechanism of failure
Excessive deposits of feedwater corrosion products such
as iron, copper or nickel oxides or oxide hydrates them-
selves are not sufficient for the development of hydrogen
damage. The second condition is the presence of acidic
contaminants in the boiler water and their concentration
underneath the deposits (e.g., by wick boiling).
A similar statement can be made with respect to any
acidic contamination in the boiler water: it alone does not
cause hydrogen damage. Here, again, a second con-
stituent is required excessive deposits beneath which
the concentration of acidic contamination may occur.
The presence of a locally acidic environment at the base
of the heavy deposits affects the magnetite growth
mechanism. Under favorable conditions (neither exces-
sive deposits on the tube surface, nor acidic contamina-
tion), the growth of the protective magnetite layer is a dif-
fusion-controlled process based on the counter-flux diffu-
sion of Fe
2+
ions towards the boiler water and O
2
ions to
the tube wall. In this way, magnetite is formed at both the
tube/oxide and oxide/boiler water interfaces; however, the
outer layer is never observed on actual boiler tubes as the
magnetite becomes incorporated into the boiler water.
The oxide which remains on the tube surface as the
indigenous oxide is stress free and thus acts as a protec-
tive layer. The growth of this protective oxide occurs para-
bolically.
At the base of the deposits, the magnetite growth pro -
cesses changes drastically under concentrating acidic
(chloride) conditions. Chloride concentrates under these
deposits and iron chloride is formed. Then the magnetite
which grows on the tube surface is not stress free and it
breaks away from the surface and another layer starts to
grow. Repetition of this process produces a thick multi-
laminated oxide structure, and the associated growth rate
changes from parabolic to a very fast linear rate. The layer
124 PowerPlant Chemistry 2010, 12(2)
PPChem 101 Boiler and HRSG Tube Failures
Features of failure
Gouged areas; thick deposits.
Thick-edged, often with "window opening" failure appearance in conventional boilers.
Longitudinal crack is the typical appearance in HP evaporators of HRSGs.
Brittle failure.
Effect on oxide and
characteristic deposits
Oxide growth under stress leads to thick, multilayer scale (alternating layers of porous
and dense magnetite), which may be missing as a result of failure incident.
Key microstructural features
Intergranular microfissures in base tube material linking to form cracks.
Decarburization at inner surface.
Multilaminated, non-protective oxide sometimes containing chloride at the tube/oxide
interface.
Root cause
Deposits formed by a number of root causes plus acidic contamination (several
sources).
Cycle chemistry implications
Source of low pH contamination (acidic) exists. Can be bulk or local concentration
only.
Inadequate instrumentation to identify contaminant ingress.
Attack rate
Very rapid (can be > 10 mm per year). Failures can occur within six months following
contamination.
Table 1:
Characteristics of hydrogen damage.
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does not growth stress-free and delaminates. Since the
hydrogen is generated at the tube surface, it all diffuses
into the tube wall and reacts with carbide (cementite,
Fe
3
C, within the pearlite structure of the carbon steel)
according to Eq. (1)
Fe
3
C + 4H 3Fe + CH
4
(1)
Methane concentrates in the tube material and causes
intergranular microfissuring at the grain boundaries. The
tube material is affected in an irreversible manner and is
embrittled. The tube material with distinctively changed
microstructure and lower strength is prone to failure. A
cross section through a boiler tube affected by hydrogen
damage showing the microcracks is shown in Figures 46.
POSSIBLE ROOT CAUSES
The most decisive root causes are all those leading to for-
mation of excessive boiler and HRSG tube deposits and
to ingress of acidic contamination in the plant cycle. Some
are briefly discussed below:
Poor feedwater treatment
typically resulting in high corrosion product levels (iron
and copper oxides or hydrated oxides). Corrosion
products generated by corrosion or flow-accelerated
corrosion in the condensate/feedwater train in conven-
tional units, and in the feedwater and in the low pres-
sure parts of the HSRG, subsequently deposit in water-
walls (conventional boilers) and in the HP evaporator
tubing (HRSGs), and form the basis of hydrogen dam-
age mechanisms.
Flow disruptions to the internal water flow inside the
boiler waterwall or HRSG HP evaporator contributing to
increased deposition of corrosion products
Adverse fireside conditions
as flame impingement and burner misalignment pro-
moting the deposition processes
Excessive deposits
being not duly detected (disregarding of tube sampling)
and not removed by chemical cleans in a timely manner
Ineffective chemical cleans
with deposits remaining on critical places
Errors in chemical cleaning process
as incompletely flushing of the cleaning solution or
flaked (not dissolved) deposits
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125 PowerPlant Chemistry 2010, 12(2)
Figure 4:
Cross section through tube with hydrogen damage showing the
microcracks.
Figure 5:
Microcracks in detail showing that the cementite (carbide
structure) is partially denuded.
Figure 6:
Microcracks in detail showing that the cementite (carbide
structure) is completely denuded.
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Minor condenser leaks
occurring over an extended period
Major condenser leaks
with a serious ingress of cooling water in the cycle
Ingress of regeneration chemicals
from upsets in makeup water treatment units or con-
densate polishers
Poor or inadequate instrumentation
not meeting the international standard for cycle chem-
istry instrumentation according to the IAPWS Technical
Guidance Document [1], which prevents having ade-
quate cycle chemistry monitoring and control to detect
contaminant ingress
FEATURES OF FAILURES
Figures 7 and 8 show hydrogen damage failures.
POSSIBLE SOLUTIONS
The possible solutions depend on the extent of damage.
For this reason, the condition of the waterwalls or the HP
evaporator tubes of a HRSG have to be evaluated.
In conventional boilers, an ultrasonic examination encom-
passing a complete scan of suspect tubing is a meaning-
ful non-destructive evaluation technique. Since most
hydrogen damage associated with boiler tubing is usually
associated with inner distress in the form of gouging to
some degree, the ultrasonic examinations essentially look
for this tube condition. This method is relatively rapid and
quite quantitative to measure the physical macrodamage
associated with hydrogen damage. However, ultrasonic
examination is not always adequate as sometimes hydro-
gen damage occurs with no wall loss. In addition, this
method does not measure the actual amount of decarburi -
zation of the affected tubing, which can lead to premature
rupture of the tubing due to low ductility. The technique
126 PowerPlant Chemistry 2010, 12(2)
PPChem 101 Boiler and HRSG Tube Failures
Figure 7:
Hydrogen damage window opening and
thick-edged failure.
Courtesy of David Daniels (M&M
Engineering Associates, Inc.).
Figure 8:
Large hydrogen damage failure.
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relies on an attenuation of the ultrasonic backwall signal
associated with the inner loss of wall. Tubes are then cat-
egorized based on the severity of the damage/wall loss
knowing that there could be additional weakened material
due to decarburization of the cementite and associated
microcracking.
The situation for HRSGs is much more difficult because
fiber optics and visual techniques are really the only non-
destructive evaluation methods which can be used other
than actual tube removal. The emphasis here must be on
minimizing the deposits by controlling the corrosion and
flow-accelerated corrosion in the lower pressure circuits.
Tube sampling in critical boiler or HRSG regions provides
information about the type, extent and thickness of
deposits. Evaluation of microsections supplies information
whether hydrogen fissures beneath of deposits are pres-
ent or not.
Immediate Actions
It is very important to react fast to any serious contami-
nant ingress in the cycle (a major condenser leak, ingress
of regeneration chemicals). Immediate shutdown is
advised in all cases when the boiler water pH was less
than 8.0 and is decreasing (this value refers to the bulk of
the boiler water as the pH beneath the deposits in con-
centrating circumstances will be markedly lower due to
the concentration of acidic contaminants). In many cases,
chemical cleaning might be required.
If evaluation of tube wastage or thinning indicated hydro-
gen damage, replacement of all affected tubes to prevent
possible ductile failures is necessary. In no case, should
pad welding or canoe/window welds be applied as repair
or replacement options in hydrogen damage situations.
Long-Term Actions
Any long-term actions for preventing hydrogen damage
have to focus on minimizing deposits buildup and avoid-
ing acidic contamination since both are required for initiat-
ing hydrogen damage.
Measures to be taken to minimize deposit buildup are
among other things:
Application of an optimum plant cycle chemistry treat-
ment to ensure a minimum corrosion product formation
and transport into the boiler.
Focus is on the feedwater in conventional plants and on
the feedwater and lower pressure circuits for HRSGs.
Use of adequate chemistry-related instrumentation and
installation of appropriate control room alarms.
Keeping deposits at an acceptable level
and if necessary removal of deposits by way of
chemical cleaning.
Removal of all geometrical flow disrupters
such as pad welds, backing rings, etc.
Periodical fireside inspections
to avoid flame impingement. A proper burner alignment
helps in reducing heat flux at critical locations.
Prevention of acidic contamination is as important as are
measures for minimizing deposit buildup. For preventing
acidic contamination, the following actions are advised:
Use of the state-of-the-art instrumentation and mini-
mum key level of instruments as specified in the IAPWS
guidance document [1] for detection of minor and major
condenser leaks and a consistent approach for their
elimination
Structural upgrade of the condenser
to eliminate major condenser leaks (replacement of
affected tubes, measures to avoid condenser tube
vibrations, etc.). As a rule, alarms in control room and
precise authoritative instructions how to proceed in the
case of a major condenser leak are advantageous.
Prevention of upsets in water treatment plants
as makeup water systems and condensate polishers.
All monitoring and alarm systems in these plants have
to be checked for reliability at regular intervals.
REFERENCES
[1] Instrumentation for Monitoring and Control of Cycle
Chemistry for Steam-Water Circuits of Fossil-fired
and Combined-cycle Power Plants, 2009. Inter -
national Association for Properties of Water and
Steam, Technical Guidance Document.
Downloadable at http://www.iapws.org/
AKNOWLEDGMENT
Wendy Weiss of the Structural Integrity Metallurgical
Laboratory in Austin, TX, U.S.A. supplied all the photo-
graphs except Figure 7.
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