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Critical Deposit Loading Thresholds for Under Deposit Corrosion in Steam

Generators

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DOI: 10.5006/4085

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SCIENCE SECTION

Critical Deposit Loading Thresholds for Under

Deposit Corrosion in Steam Generators

A. Ramesh,* N. Laycock,‡,* P. Shenai,** A. Barnes,*** H. Van Santen,*** A. Thyagarajan,**

A. M. Abdullah,**** and M.P. Ryan*****

Significant industrial facilities typically operate a steam system with multiple steam generators (or boilers) that are potentially vulnerable to

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under deposit corrosion (UDC). This mechanism begins with the deposition of a porous layer of magnetite particles on the waterside heat
transfer surfaces. Beneath this layer, wick-boiling causes the concentration of contaminants (such as chlorides) until the concentration
exceeds some critical threshold that results in rapid corrosion. Industry practice to mitigate this risk includes monitoring the extent of
deposition and then chemically cleaning the equipment before the deposits reach the critical level. One significant factor in this mechanism
is the heat flux, which drives both the magnetite deposition and the wick-boiling processes. This paper investigates the relationship between
heat flux and the critical deposit thickness for the initiation of chloride-driven UDC. Ex-service samples from industrial steam generators
have been examined, an electrochemical method has been developed for in situ measurement of the deposit loading, and a wick-boiling model
has been used to estimate the local conditions beneath the porous deposits during the progress of UDC. For 1.0 Cr 0.5 Mo steel coils from a
steam generator operating at approximately 75 bar(a) under an all volatile treatment regime, the threshold for the onset of rapid UDC was
determined to be at a heat flux of 350 kW/m2, deposit loading of approximately 50 mg/cm2, and deposit thickness of approximately 95 μm,
corresponding to a local chloride concentration beneath the deposits of approximately 80 ppm and a local at-temperature pH below ∼2.7.

KEY WORDS: boiler, deposit, pitting, steam, under deposit corrosion

INTRODUCTION (i) caustic gouging;4 (ii) acid phosphate corrosion;5 and

A lmost all significant industrial facilities operate a large
steam system comprising multiple steam generators
(typically waste heat boilers, cooling the main process stream)
and multiple steam users (including both heat exchangers using
steam to heat the main process flow and turbines generating
electrical power). Various components of these systems are
potentially vulnerable to different damage mechanisms, such
as corrosion fatigue in the deaerator vessels, flow-assisted
corrosion (FAC) in the feedwater piping, under deposit cor-
rosion (UDC) in the evaporator tubes, and stress corrosion
cracking (SCC) of turbine blades. To mitigate these threats,
water chemistry throughout the system must be rigorously
controlled and guidelines for such controlled conditions are
provided by several different organizations.1-3 However, it must
be noted that these guidelines are developed for commercial
power plants and not specifically for industrial production sites.
Power plants are usually compact in design with a high focus
on energy efficiency, while industrial systems can be very much
larger, and the design details significantly different, such that
blanket adoption of power industry guidelines may not always
lead to the desired outcomes.
Historically, three different types of UDC have affected
the evaporator tubes in high-pressure steam generators:
(iii) chloride-driven UDC (which may subsequently lead to failure
by hydrogen damage).6-7 The primary cause of UDC is the
deposition of a porous layer of magnetite particles on the
waterside surface of the evaporator tubes. The magnetite
particles are generated by FAC elsewhere in the system
(e.g., in the feedwater piping) and then transported into the
steam generator, where they deposit on the heat transfer sur-
faces.2,8-11 Beneath this layer, a wick-boiling process leads to
concentration of nonvolatile contaminants present in the water.
As the deposits become thicker, the degree of concentration
can reach factors as high as 10,000 times the bulk concentra-
tion.2 At some point, the concentration reaches a critical
threshold level and causes the initiation of UDC. Depending on
the initial composition of the steam generator water, this may
be any of the three types mentioned above. Over the last 20 y or
30 y, chloride-driven UDC has become an increasingly prev-
alent failure mode as a result of the drive for higher performance
(leading to increased flow velocities in the feedwater piping
and higher heat fluxes in the evaporators); the trend away from
phosphate-based water treatment toward all volatile treat-
ments (AVT); and the increasing use of air-cooled condensers
(ACCs). ACCs have a very large surface area and are prone
both to FAC during operation and oxygen corrosion during
downtime, both of which lead to increased levels of magnetite

Submitted for publication: March 10, 2022. Revised and accepted: April 25, 2022. Preprint available online: April 25, 2022, https://doi.org/10.5006/4085.
‡
Corresponding author. E-mail: nick.laycock@shell.com.
*Qatar Shell Research and Technology Centre, Qatar Science and Technology Park, Doha 24750, Qatar.
**Shell Technology Centre Bangalore, Bengaluru 562149, India.
***Shell Technology Centre Amsterdam, Grasweg 31, 1031 HW Amsterdam, The Netherlands.
****Center for Advanced Materials, Qatar University, P. O. Box 2713, Doha, Qatar.
*****Department of Materials and London Centre for Nanotechnology, Imperial College London, South Kensington Campus, Exhibition Road, SW7 2AG London,
United Kingdom.

ISSN 0010-9312 (print), 1938-159X (online) © 2022 AMPP.

584 JULY 2022 • Vol. 78 • Issue 7 Reproduction or redistribution of this article in any form CORROSIONJOURNAL.ORG
is prohibited without express permission from the publisher.
 SCIENCE SECTION

particles in the feedwater and hence to an increased risk of
UDC. These three trends have led to a significant increase in
the number of failures due to UDC—especially those related to
hydrogen damage (i.e., chloride-driven UDC), as reported by
57% of respondents to an Electric Power Research Institute
(EPRI) survey in 2001, compared to 37% in 1997.12 The heat
flux varies widely between different types of steam generator,
with peak values in conventional power generation typically
ranging from13 147 kW/m2 to 473 kW/m2, compared to the
maximum value of approximately 550 kW/m2 for the petro-
chemical waste heat boiler considered in this paper.
The practices recommended to mitigate the risks of
chloride-driven UDC are described by EPRI,2 the International
Association for the Properties of Water and Steam (IAPWS)1,11
and industry publications,6 with minor differences limited to small
variations in recommended operating windows. In broad
scope for significant errors in decision making, potentially
resulting in excessive cost and lost production due to “early”
cleaning, or tube failures and lost production due to failure to
clean in time. In this paper, we describe an investigation into
the relationship between heat flux and the critical deposit
thickness for initiation of UDC. The work includes the exami-
nation of coils removed from a selection of industrial waste heat
boilers that had suffered from UDC, together with the devel-
opment of a model for the local chemistry changes that occur
beneath the deposits.
EXPERIMENTAL PROCEDURES
2.1 | Materials
The samples for this work were taken from a group of

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nominally identical boilers in parallel service, all of which had
terms, the requirements are to manage feedwater quality to suffered from UDC. The boilers are of a helical coil design,27-28
minimize the risk of FAC14 and hence reduce the amount of with hot process gas on the inside of the coils and boiling water
iron (both dissolved ferrous ions and solid magnetite particles) on the outside, as shown in Figure 1. The coil material is DIN
that enters the steam generator; to minimize the chloride 1.7335, a 1.0 Cr 0.5 Mo low alloy steel, with the nominal
concentration in the steam generator water; and, finally, to composition shown in Table 1. Twelve sections of coil were
monitor the extent of deposition and complete a chemical obtained from four boilers, with each section being approxi-
clean before the deposits reach the levels necessary to mately 1 m in length. The selection of these sections was
initiate UDC. largely based on accessibility, though visual inspection showed
While various factors influence the deposition rate (Ȧ) on that significant UDC was present in all cases.
the waterside surfaces of heat exchangers, it is commonly
observed to be most strongly governed by the heat flux (Q).
2.2 | Deposit Loading Measurements
Detailed studies in the literature have found a linear dependence
The usual industrial method for measuring deposit
for haematite deposition on Zircalloy 2 at ambient pressure15
loading is to remove a boiler tube that has been in service, and
as well as at moderate pressures of 10 bar,16 while data from
then take a small section of that tube; weigh it; clean it; then
high-pressure boilers suggested a proportionality of Ȧ to
weigh it again and calculate the deposit loading (in mg/cm2)
Q2.17-20 Recirculating loop experiments at subcooled conditions
based on the mass of material removed by cleaning. The
(i.e., below the boiling point) also showed that the deposition
cleaning can be accomplished using inhibited acid solutions,
rate followed a squared dependence on the heat flux over a short
glass bead blasting, or other mechanical methods.11,29
timescale of 10 h.21 Over a longer timescale of 800 h, the
model by Lister and Cussac predicts the deposition rate will taper
off in the subcooled regime but continue to maintain higher C. Steam
values under bulk boiling conditions.22 Margulova and Belyaev23
showed that in once-through subcritical boilers, the deposition
rate at 250 kW/m2 to 300 kW/m2 was more than an order of
magnitude higher than that at 50 kW/m2 to 60 kW/m2.24-25
In general, the consensus is a linear dependence of Ȧ on the
concentration of Fe in the boiler water and a power-
dependence on the heat flux, with an exponent varying
between 1 and 3.5.8,26
The current industry guidance is focused on heat re-
covery steam generators (HRSGs).2,11 Important features of the
advice are the methods for monitoring deposit loading and the
definition of the critical loading value at which cleaning is re-
quired. There have also been a number of laboratory-based B. Blowdown
attempts to reproduce the deposition process and support the
development or validation of theoretical models,8-10 but these
have to date proved incapable of matching industrial deposition
rates. Hence, the industry continues to rely on a destructive
examination of tubes removed from the highest heat-flux zones A. Boiler feed water
of the boilers. For the critical deposit loading threshold, both
EPRI and IAPWS suggest experience-based values of around
35 mg/cm2 as a maximum level before cleaning is required.
However, there are expected to be significant differences for
other types of steam generators, due to variation in factors D. Heating medium
such as the pressure, heat flux, circulation rate, and whether the FIGURE 1. Schematic of an industrial steam generator, with a helical
water is inside or outside the tubes. Consequently, especially coil design. The water inside the boiler is known as boiler water (BW)
for high heat-flux industrial steam generators operating outside and is more concentrated than the boiler feed water (BFW) but has the
the conditions typical of power generation facilities, there is same composition as the blowdown.

CORROSIONJOURNAL.ORG JULY 2022 • Vol. 78 • Issue 7 585

SCIENCE SECTION
Table 1. Nominal Composition of the Steam Generator
Coils [DIN 1.7335]
Element Wt%
Carbon 0.1–0.18
Chromium 0.7–1.0
Manganese 0.4–0.7
Molybdenum 0.4–0.5
Phosphorus ≤0.04
Sulfur ≤0.04
Silicon 0.15–0.35
The present work adopted the acid cleaning technique, using
a solution of 7 wt% HCl (Suprapur†, Sigma Aldrich) with 20 g/L
of hexamine added as a corrosion inhibitor. During cleaning, the
samples were also cathodically protected using an external
power supply (MCH-K305DP†, MCH Instrumentation) to maintain
a potential difference of 6 V between the sample and a Pt wire
counter electrode inserted in the cell. Initially, a small rectangular
sample (surface area ∼8.5 cm2) was cut from one of the coils,
then wet ground to a smooth finish and dried in laboratory air.
This coupon was weighed and exposed to the inhibited acid in
a glass beaker, with applied cathodic protection. Cleaning was
performed for 30 min, and then the sample was dried and
reweighed. Following these initial tests, an electrochemical cell
was then designed to fit on the curved external surface of a
coil, exposing only a small part of the coil surface (∼2.4 cm2)
to the test solution during any given measurement; see Fig-
ure 2. This design enabled measurements to be taken at different
locations around the circumference of each coil, which helped
enable measurements over a wide range of heat-flux values
(as explained in more detail later in this paper). For each
measurement, the cell was filled with the inhibited acid and the
sample was cathodically protected, as described above. After
each measurement, the used electrolyte was drained from the
cell through the drain line and collected for analysis. The
collected fluid was filtered using Whatman† Grade GF/C glass
microfiber filter paper (WH1825-047), which retains particles
up to 0.7 μm diameter, and subsequently analyzed for dissolved
Fe concentration using an Agilent 5110† inductively coupled
plasma optical emission spectrometer (ICP-OES). The filtrate was
weighed and then examined in a scanning electron micro-
scope equipped with energy dispersive x-ray analysis (SEM-EDX,
FEI Quanta FEG 250†). Several samples of deposit were also
analyzed using x-ray diffraction (XRD). The combination of EDX
and XRD has shown the deposits to be composed almost
entirely of magnetite (Fe3O4), with the presence of only minor
levels of contaminant species such as chlorides. Conse-
quently, the collected solids and the dissolved Fe are assumed to
have been originally present on the coil surface as Fe3O4, and
hence the total deposit loading is calculated in mg/cm2 (as Fe3O4)
from the sum of the mass of the removed solids and the mass
of the dissolved Fe that was present in the collected liquids.
During the initial development of this technique, some
experiments were performed in which a 1 mL sample of
the cleaning liquid was removed every 2 min for analysis, and
the solution replenished with demineralized water. Based on the
results of these initial experiments (as discussed later in this
†
Trade name.
586 JULY 2022 • Vol. 78 • Issue 7
paper), the cleaning period for subsequent measurements was
set at 15 min.
2.3 | Metallography
Small samples were cut from the coils to enable viewing
of the external (waterside) surface of the coils in cross section.
For each location along the length of the coil at which any
sample was taken, samples were prepared from four positions
around the circumference, with the extrados (outside of the
coil bend) defined as the 0° datum point and the other samples
being from 90° (top), 180° (intrados), and 270° (bottom) posi-
tions. These samples were mounted in Struers† multifast
thermosetting resin (Cleveland, OH, USA) using a Struers
CitoPress-15 mounting machine, to show a cross-sectional view
of the external coil surface, each one covering approximately
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1 cm to 2 cm around the circumference. The cross sections were
successively ground using 120 to 2000 grit paper, and then
polished using a 1 μm diamond paste together with Struers
Tegramin 25 grinding and polishing equipment. Finally, the
samples were etched using 2% Nital.30 They were then examined
using a Zeiss Axio Vert A1† optical microscope (Jena,
Germany) and SEM-EDX. In total, 48 samples (four from each of
the 12 original coil sections) were prepared for analysis. On
each of these samples, the thickness of any surface layers was
measured using an optical microscope equipped with Zeiss
Zen Lite™† Software (Jena, Germany). Small samples of the
surface deposits were also scraped from some samples (using
a scalpel) and analyzed using SEM-EDX and Powder XRD.
RESULTS AND DISCUSSION
3.1 | Characteristics of Under Deposit Corrosion
These exchangers were in parallel service with hot pro-
cess gas on the inside of the coils and boiling water on the
outside, at approximately 75 bar(a) and 290°C. The water
chemistry for this system was controlled using an AVT of the
BFW with the operating window based on guidelines published
by the VGB,3 but with small variations. Chloride levels in the
feedwater were typically 2 ppb to 3 ppb, giving 100 ppb to
150 ppb in the boiler water. The intent of this water treatment is
to ensure that steel surfaces exposed to water anywhere in the
steam cycle (including feedwater, boiler water, steam, and
condensate systems) are protected from corrosion by a thin
surface film of magnetite.2,14 Examination of the sample coils
clearly shows the well-known characteristics of chloride-
driven UDC, including the presence of a powdery black deposit
over the waterside surface of the coils, and multilayer scales of
corrosion products over the most corroded locations (Figure 3).
Both the powdery deposit and the multilayer scales were
found to consist predominantly of Fe and O, and XRD (Figure 4)
revealed the crystalline material to be almost completely
magnetite (Fe3O4). There were also signs of chloride contami-
nation within the corrosion products (Figure 4), though the high
solubility of chloride salts combined with the wet polishing
method used to prepare these samples means that most of
the chlorides were likely dissolved and removed during the
sample preparation.
Corrosion was observed along a significant length of the
coils, with the most severe corrosion being generally closer to
the inlet end (where the hot process gas enters the coils).
Samples for this work were only obtained from the inlet half of
the coils, where most corrosion was observed. However, it was
also noticed that severe corrosion was found only on the
extrados, with initial visual inspection suggesting there was no
CORROSIONJOURNAL.ORG

Metal wire and magnet
–ve
Power supply Boiler tube
(cathode)
+ve
Platinum wire
(anode) O-ring
Deposit removal
solution
PTFE cell
Drain line
FIGURE 2. The electrochemical cell used for deposit loading measurements. The cell is fabricated from polytetrafluoroethylene (PTFE) and a
rubber o-ring is used to form a seal against the coil surface, with cable ties wrapped around the coil to pull the cell against the surface and enable
a good seal between the o-ring and coil.
5 mm
(a)
FIGURE 3. (a) Cross section through part of a coil suffering from severe UDC; and (b) higher magnification cross section through the same
corroded area, showing the multilaminated scale characteristic of chloride-driven UDC.
significant corrosion whatsoever on the intrados. For some of the
metallurgical cross sections, the thickness of the surface
deposit layer was measured at approximately 10 μm to 20 μm
intervals across the ∼2 cm width of the sample, then the
sample was ground back for approximately 0.5 mm to 1 mm and
repolished, then another set of measurements was taken, and
this procedure was repeated four or five times. As shown in
Figure 5, the deposit thickness can vary quite significantly over
this small sample area, which is consistent with the visual as-
sessment of the coils before they were prepared for metal-
lurgical analysis. It was not feasible to complete this large number
of measurements on all samples and hence it was decided for
the remaining samples that the thickest deposit on each sample
would be identified by visual assessment and then at only that
location would a measurement be taken. This is the most
conservative approach in terms of assessing the potential for
UDC and is considered complementary to the deposit loading
measurements, which determine an average value across the
sampled area.
Optical characterization of the deposits indicates that
progression of UDC falls into four distinct stages, as shown in
Figure 6. Stage 1 represents the initial condition, with the steel
CORROSIONJOURNAL.ORG
SCIENCE SECTION
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50 Pm
(b)
surface passivated by a thin layer of magnetite. Samples in this
stage show an adherent, nonporous layer adjacent to the steel
surface, with no more than two clearly distinguishable surface
layers, no signs of spallation (i.e., fractures within the scale),
and with any pitting ≪100 μm in magnitude. Stage 2 involves the
development of a porous deposit layer on top of the original
magnetite. Samples in this stage show at least two distinct
surface layers, with some evidence of porosity in the outer
layer, but they do not show clear evidence of multiple corrosion
product layers and pitting remains <100 μm. Stage 3 clearly
shows the development of multilayer scales of corrosion pro-
ducts, but the pitting remains <100 μm. Stage 4 is the final
stage, defined by thick multilayer scales of corrosion product,
with clear evidence of significant spallation (i.e., fractures
between the layers of corrosion products) and typically with
pitting ≫100 μm. There is a level of subjectivity when making
this assessment, but the overall progression is generally clear.
On this basis, the observed circumferential variation in cor-
rosion severity is shown in Figure 7. Stage 4 UDC was found only
on samples from the extrados (0°), and all of the extrados
samples were assessed as stage 3 or 4. In contrast, all samples
from the intrados (180°) were found to be in stage 1 or 2.
JULY 2022 • Vol. 78 • Issue 7 587
SCIENCE SECTION

70

60

Number of Measurements
50

40

30

20

10
SE
Map data 405 40 Pm 0

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SE MAG: 1,224× HV: 20 kV WD: 9.9 mm

(31, 32]
(33, 34]
(35, 36]
(37, 38]
(39, 40]
(41, 42]
(43, 44]
(45, 46]
(47, 48]
(49, 50]
(51, 52]
(53, 54]
(55, 56]
(57, 58]
(59, 60]
(61, 62]
(63, 64]
(65, 66]
(67, 68]
(69, 70]
(71, 72]
(73, 74]
(75, 76]
(77, 78]
(79, 80]
(81, 82]
(83, 84]
(85, 86]
(87, 88]
d30
(a)
Deposit Thickness (Pm)
(a)
30

Number of Measurements 25
Fe O
40 Pm 40 Pm
20
(b) (c)
15

10

5
O Cr
40 Pm 40 Pm
0
(3, 4]
(5, 6]
(7, 8]
(9, 10]
(11, 12]
(13, 14]
(15, 16]
(17, 18]
(19, 20]
(21, 22]
(23, 24]
(25, 26]
(27, 28]
(29, 30]
(31, 32]
(33, 34]
(35, 32]
(37, 38]
(39, 40]
(41, 42]
(43, 44]
(45, 46]
(47, 48]
(49, 50]
(51, 52]
(53, 54]
(55, 56]
(57, 58]
(59, 60]
(61, 62]
(63, 64]
(65, 66]
(67, 68]
(69, 70]
(71, 72]
(73, 74]
(75, 76]
(77, 78]
(79, 80]
>80]
(d) (e)

11,000
Boiler tubes
PDF 00-011-0614 Fe3O4 magnetite
Pm)
Deposit Thickness (P
10,000 (b)
9,000 FIGURE 5. (a) and (b) Histograms showing the variation of the deposit
8,000 thickness on two samples. Each histogram shows all of the measure-
7,000 ments from one sample about 2 cm in width. The deposit thickness
was measured at approximately 10 μm to 20 μm intervals across the
Counts

6,000
sample, then the sample was ground back for approximately 0.5 mm
5,000
to 1 mm and repolished, then another set of measurements was taken,
4,000 and this procedure was repeated four or five times.
3,000
2,000
at the operating pressure. The heat flux decreases as the process
1,000 gas is cooled, but for helical coil heat exchangers there is also a
0 strong circumferential variation due to the centrifugal forces
10 20 30 40 50 60 70 80
T (Coupled 2T/T) WL = 1.54060
2T acting on the tube-side fluid, which means that the heat flux is
(f) always higher at the extrados.26-27 For the waste heat boiler coils
considered in this paper, this leads to an overall variation in heat
FIGURE 4. SEM/EDX images showing the presence of chloride within flux (which is calculated as part of the equipment design), as shown
the scale: (a) SEM image; (b) Fe map; (c) Cl map; (d) O map; (e) Cr map;
in Figure 8. The magnitude of the heat flux is known to impact
and (f) XRD spectrum showing the presence of magnetite.
UDC through effects both on the rate of formation of the porous
The explanation for this result lies in consideration of the deposit layer and on the wick-boiling process.
heat flux, which is a measure of the rate of energy transfer from the
hot process gas to the boiling water. The process gas is cooled 3.2 | Deposit Loading
as it passes through the coils, while the temperature of the water To demonstrate that the acid cleaning step of the deposit
on the other side of the coils is fixed at the boiling point of water loading measurement method did not cause significant corrosion

588 JULY 2022 • Vol. 78 • Issue 7 CORROSIONJOURNAL.ORG

 SCIENCE SECTION

Stage 1 Stage 2 Stage 3 Stage 4

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50 P 50 P 50 P 50 P

50 P 50 P 50 P 50 P

FIGURE 6. Schematic showing the four stages of UDC, together with representative optical microscopy images of samples that have been
classified in each of these stages. These images are about 200 μm wide, but the UDC stage classification for a given sample is based on
assessment of the entire sample, which is approximately 2 cm wide.

12 600 Extrados Intrados

Top and bottom
0° 90° 180° 270° 500
Number of Samples (n)

10
Heat Flux (kW/m2)

400
8
300
6
200
4
100
2
0
0 0 20 40 60 80 100
1 2 3 4 Length Along The Coil (m)
Stage of UDC FIGURE 8. Variation in heat flux along the length of the steam
FIGURE 7. The percentage of samples at each angular location (0°, generator coils for different positions around the coil circumference
90°, 180°, and 270°) that were determined to be in each stage of UDC. from the extrados (0°) through to the intrados (180°), per the proprie-
Note that the extrados (0°) is the highest heat-flux location, and the tary design. Note that the lines for “top” and “bottom” are coincidental.
intrados (180°) is the lowest.

location visually assessed as being in stage 3 and the other in

of the underlying steel, a bare steel coupon with no surface
deposits was first used for weight loss measurements. Over a
30-min cleaning period, the average corrosion rate was ap-
proximately 3 μm/y, contributing approximately 1 μg of Fe to the
test solution, compared to deposit loadings on field samples
that are typically in the range of 10 mg/cm2 to 60 mg/cm2. Further
demonstration tests were then performed using the experi-
mental arrangement shown in Figure 2, using coil samples that
were initially covered by deposits and corrosion products.
Figure 9 shows measurements of the total Fe level in 1 mL
samples extracted from the test solution roughly every 2 min
during surface cleaning at two separate trial locations, with one
stage 4 UDC. For each location, the rate of Fe release is highest in
the first few minutes of the acid cleaning. The deposit removal
rate was also different at the two trial locations, which is likely due
to differences in porosity—which translate to differences in
the density of the material being removed. Subsequent tests with
only 15 min cleaning periods always revealed clean surfaces at
the end of the test. Hence, it is considered that a 15 min cleaning
period was sufficient to ensure removal of any reasonably
expected level of surface deposits. However, as shown by the
linear regression lines in Figure 9, the increase in Fe level after
15 min was relatively slow, but not zero, corresponding to an
apparent residual corrosion rate of about 4 mm/y. This is

CORROSIONJOURNAL.ORG JULY 2022 • Vol. 78 • Issue 7 589

SCIENCE SECTION

18 Theoretical heat flux

Deposit thickness
y = 0.2116x + 6.4196 100.0 Deposit loading
15
R2 = 0.9343

12
Total Fe (ppm)

y = 0.7724x + 0.5965 80.0

R2 = 0.5819
9
60.0
6 y = 0.2254x + 2.8677

%
R2 = 0.9388
3 y = 0.4909x - 0.3025 40.0
R2 = 0.9378
0
0 5 10 15 20 25 30 35 20.0
Time (min)
FIGURE 9. Measurements of the total Fe level in 1 mL samples
0.0

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extracted from the test solution roughly every 2 min to 3 min during
surface cleaning at two separate trial locations: red markers are for a
location in stage 3 UDC, and blue markers for a location in stage 4
UDC. Separate trend lines are shown for the first 15 min and second
15 min of each experiment.
significantly higher than measured in the weight loss experiments
and possibly reflects crevice corrosion around the edges of
the o-ring seal but may also result from relatively slow transport
of removed deposits from the main cell compartment into the
drain line from which small samples were taken during the test.
Based on these results we selected a 15 min cleaning duration
for subsequent deposit loading assessments, to ensure removal
of all surface deposits within the sample area while minimizing
any errors from potential corrosion of the underlying steel.
Demineralized water was also used after each cleaning period
to thoroughly rinse the cell through the drain line, and this rinsing
liquid was included as part of the sample used to determine the
total amount of removed deposit. This method has potential
industrial applications in situations where coil or tube removal
is unfeasible but where access to the waterside surface of the
tube or coil is possible.
The developed procedure was then utilized to measure
the deposit loading (mg/cm2) on the sample coils at locations
immediately adjacent to those from where the metallographic
samples were taken (on which the deposit thickness was mea-
sured). Figure 10 shows the variation of the design heat flux,
deposit loading, and deposit thickness as a function of position
around the circumference, with each value normalized to the
maximum at that position along the coil length. It is important to
understand here that the heat flux is determined by the design
and operation of the steam generator, while the deposition
process depends on the heat flux together with the compo-
sition and flowing dynamics of the boiler water. Figure 10 shows
–90 0 90 180 270 360
Angular Location Around the Coil Circumference (degree)
FIGURE 10. Variation of heat flux, deposit loading, and deposit thick-
ness as a function position around the coil circumference. All data are
normalized by taking the results at 0° on each individual sample to be
100%. Error bars represent the standard deviation of the measured
values and all results are for cardinal positions (0°, 90°, 180°, and 270°),
but a small degree of jitter has been used to separate the error bars
for deposit loading and deposit thickness.
to assess the extent of deposition and ensure that cleaning is
performed before the onset of rapid UDC, i.e., before the cor-
rosion process enters stage 4. Hence, taking into account only
the samples in stages 1 to 3, Figure 11 shows the dependence of
loading on heat flux. Again, these results show that the loading
increases with heat flux, but the data are widely scattered and
there is no clear relationship that could be confidently used for
predictive purposes, which is consistent with the wide range of
power laws reported in the literature.8
3.3 | Wick-Boiling and the Critical Deposit Threshold
for Under Deposit Corrosion
In addition to knowing the absolute deposit loading, it is
also necessary to know the critical loading value above which the
risk of rapid UDC is considered “too high.” This critical value
will depend on other factors, and different approaches to this
issue have been taken by different industry bodies. Some
present the cleaning threshold as a function of boiler pres-
sure,2,11 while others13,31-32 use the heat flux. For the steam
70
Deposit Loading (mg/cm2)

60
that, as expected, both the loading and thickness increase with
y = 0.0817x + 4.737
heat flux. If the deposits are homogeneous (i.e., in their com- 50
R2 = 0.2521
position and porosity), then the deposit loading (in mg/cm2) will
40
be a fixed multiple of the deposit thickness (in μm). However, it
must be recognized that the surface “deposits” measured in 30
this work can include the original protective magnetite film; any
porous layer that is deposited on top of this film; and then any 20
corrosion products that are produced if the final rapid stage of 10
UDC has been reached. The correlation between loading and
thickness in these results is quite weak, consistent with the 0
0 50 100 150 200 250 300 350 400 450
IAPWS guidelines1,11 that state there is no accepted universal
correlation factor for this relationship. This is discussed in more Heat Flux (kW/m2)
detail later in this paper. Nonetheless, as mentioned earlier, the FIGURE 11. Measured deposit loading vs. heat flux for samples
practical purpose of deposit loading measurements is primarily assessed to be in stages 1 to 3 of UDC.

590 JULY 2022 • Vol. 78 • Issue 7 CORROSIONJOURNAL.ORG

 SCIENCE SECTION

generators considered in this paper, the operating pressure of
approximately 75 bar corresponds to a recommendation that
cleaning is required before a deposit loading of approximately
35 mg/cm2,2,11 while the maximum heat flux of approximately
550 kW/m2 corresponds to the maximum allowable deposit
loadings of approximately 25 mg/cm213,32 to approximately
55 mg/cm2.13,31 Because of the helical coil design of the steam
generators considered in this work, measurements from dif-
ferent positions around the circumference of the coil provide an
opportunity to assess the transition to stage 4 as a function of
heat flux. At a given point along the coil length, the amount of
deposit (and hence the progression of UDC) would be
expected to increase as the heat flux increases from the intrados
toward the extrados. Consequently, from measurements taken
around the circumference of the coils at several different loca-
values measured for any given UDC stage, and this is greatest
for stage 4 where spalling of corrosion products had occurred on
some parts of the sampled areas. Nonetheless, the highest
stage 3 loading result is approximately 55 mg/cm2, and all but one
of the stage 4 results exceed 49 mg/cm2, suggesting a
threshold of approximately 50 mg/cm2. For deposit thickness,
the readings are the maximum value measured for each
sample, and so do not suffer as much from variation due to
spallation, and hence the picture is a little clearer; the highest
stage 3 reading is approximately 90 μm and the lowest stage 4
reading is at approximately 95 μm. Thus, the ratio between the
thresholds in thickness and loading is approximately 1.9, es-
sentially equal to that calculated for nonporous magnetite (i.e.,
1.93). For heat flux, there is some overlap of stage 3 and stage 4
results, but the lowest stage 4 result suggests a threshold at
approximately 350 kW/m2.

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tions along their length, Figure 12 shows the assessed stage
of UDC as functions of the heat flux, loading, and thickness. The
aim of these plots is to help identify the thresholds at which the
transition occurred from stage 3 to stage 4 UDC. As expected,
the stage of UDC generally increases with increasing deposit
loading. However, there is quite some scatter in the loading
5 combination of mechanical deaeration and chemical oxygen
4
UDC Stages
It is important to note that the corrosion of the steel is
caused by the local chemical conditions beneath the deposit, and
so these apparent thresholds for the onset of stage 4 UDC
must depend to some degree on the bulk water chemistry.
In an industrial steam system, the boiler feedwater is first
demineralized by passing through polishing beds filled with
ion-exchange resins, then deoxygenated (typically by a
scavengers), and then dosed with other chemicals for pH

control. For an AVT regime such as that used in the systems

3 considered here, the pH is controlled using a proprietary
mixture of volatile amines, sometimes with supplemental am-
2 monia injection if required to meet applicable pH targets
throughout the system. The demineralization process typically
1 results in residual traces of NaOH or HCl, with their levels
monitored using a range of online sensors combined with manual
0
samples and laboratory analysis. Given the expected operating
0 20 40 60 80
performance for the system considered here, the chloride level in
Deposit Loading (mg/cm2)
the feedwater is typically <3 ppb. The boilers then typically
(a) operate at about 50 cycles of concentration so that chloride
5
levels in the bulk boiler water will be <150 ppb, while the bulk
pH (measured at room temperature) will generally be at the higher
4
UDC Stages

end of the 9 to 9.5 target range, as shown in Table 2. If wick-

3 boiling occurs beneath surface deposits, then the volatile amines
and ammonia are predominantly evaporated out of the
2 aqueous phase, leaving behind a solution that consists mainly of
the nonvolatile contaminant species. As shown in Table 3,
1 calculations reported by EPRI2 show that boiler water containing
only 310 ppb ammonia and 50 ppb chloride will have a room
0 temperature pH of 9.0. For a boiler water temperature of 300°C,
0 30 60 90 120 150
where the neutral pH is approximately 5.7, this same solution
Pm)
Deposit Thickness (P
will have a pH of 5.7, but if wick-boiling leads to concentration by
(b) a factor of 1,000 beneath the deposits, then the pH (at 300°C)
5
beneath those deposits will fall to 3.7. Adding sodium ions into
4 this mixture will increase the pH, but with an excess of chloride
UDC Stages

over sodium the concentrated solution will always be acidic.

3

2 Table 2. Nominal Operating Window for the BFW and BW

1 Parameters BFW BW
pH at 25°C 9.1–9.5 9.0–9.5
0
0 100 200 300 400 500 Specific conductivity (μS/cm) 2–5 <15
Heat Flux (kW/m2) Dissolved oxygen (ppb) <20 –
(c)
Total organic carbon (ppm) <1 –
FIGURE 12. The assessed stage of UDC for each sample as a function
Chloride (ppb) 2–3 100–150
of: (a) deposit loading; (b) deposit thickness; and (c) heat flux.

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SCIENCE SECTION

For CANDU pressurized water reactors, there was a

Table 3. Comparison of the Computed pH in this Work and
detailed investigation33 into the potential for UDC beneath the
the Measured pH at Different BW Compositions12
sludge piles that build up on the upward-facing bottom
(bracketed values)
tubesheet in the waterside of the recirculating steam generators.
Experimentally, they demonstrated that the concentration BW Composition (BWC) pH (at 25°C) pH (at 300°C)
factor beneath these deposits increased with the heat flux and BWC1: 0.310 ppm NH3 and 8.99 (9.0) 5.68 (5.7)
the depth of the deposit. Because of developing transport 0.05 ppm Cl−
limitations, very deep piles became less efficient at enabling this
BWC2: 0.280 ppm NH3; 0.05 ppm 8.99 (9.0) 5.76 (5.8)
contaminant concentration, but this did not occur until pile
Cl− and 0.025 ppm Na+
depths exceeded 50 mm and hence is not relevant to the
discussion here. They also developed a theoretical model for
the concentration process, which is shown schematically in For any contaminant species, the concentration factor
Figure 13. (CF) is the ratio of its concentration beneath the deposits to its
Water flows through the porous deposit layer to the hot concentration in the bulk, which can be determined by rear-
metal surface where boiling takes place. The resulting steam ranging Equation (1) to give
bubbles then flow back through the deposit through “chimney-

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like” passages. Contaminants are transported to the hot surface
CðLdep Þ 1
with the water by convection, and can then be transported =   (2)
Cð0Þ
away by diffusion, in droplets of water entrained with the steam, ðH þ εE Þ þ ð1 − ðH þ εE ÞÞ exp − Φτ C1cov ΔHvQρw,l D Ldep
or by vaporization. For a given thickness of deposit, the
steady-state condition is reached when the efflux of contami-
For fully dissociated ionic species such as chlorides,
nants balances the influx, as shown by Equation (1) (for which a
vaporization, and entrainment are considered negligible (see
complete derivation is provided in Appendix A)
Appendix A), and hence Equation (2) reduces to
φD dCðxÞ 1 Q 1 Q  
− þ × CðxÞ= ðH þ εE Þ CðLdep Þ Q
τ dx Ccov ΔHv ρw,l Ccov ΔHv ρw,l = exp α × Ldep (3)
Cð0Þ ρw × ΔHv × D
× CðLdep Þ (1)
where the factor α is given by
where Φ is dimensionless porosity; τ is dimensioness tortu-
τ 1
osity; D is molecular diffusion constant in m2/s; C(x) is concen- α= (4)
tration at depth x in the layer (0 is the water interface, Ldep is at Φ Ccov
the tube wall interface) in mole/m3; Ccov is a dimensionless
As shown in Figure 14, the calculated concentration
coverage factor indicating the fraction of the surface that is
factor is very sensitive to the selection of the parameters that
covered by the porous layer (i.e., the area that is not occupied by
define the value of α, which relates to the physical properties
the “chimneys” that allow steam to escape from the metal
of the deposit. For the calculations presented here, the esti-
surface); Q is heat flux in W/m2; ρw,l is liquid water density in kg/
mation of porosity will be discussed in more detail shortly. In
m3; ΔHv is vaporization enthalpy in J/kg; H is Henry constant in
the subsequent calculations, the tortuosity is calculated from the
mole/mole; εE is entrainment coefficient kg/kg; and Ldep is layer
porosity according to Equation (5), a relationship commonly
thickness in m.
used for tortuous flow in porous media.34 Finally, for the coverage
factor, values from 0.86 to 0.98 (i.e., 86% to 98% coverage)
have been considered,35 and here we have selected a repre-
C(0) sentative value of 0.9.
C
Flow of water with velocity U
Flow of water + contaminants

τ = 1 þ 0.8 × ð1 − ϕÞ (5)
Diffusion of contaminants
Diffusion of contaminants

Steam + entrainment

The estimated porosity value is thus critical for these

Ldep
Porous layer
Hot wall
FIGURE 13. Schematic diagram to explain the wick-boiling model, with
the transport of nonvolatile contaminants (such as chlorides) to the
hot surface in the flow of water through the porous surface layer, then
transport of the water away from the surface as steam (through
“chimneys” in the surface layer), while the nonvolatile contaminant
species are primarily transported away from the hot wall only by
diffusion through the water in the porous layer.
calculations. As discussed earlier, the measured deposit loading
and deposit thickness are quite poorly correlated, whereas
under ideal conditions they should exhibit a linear correlation
dictated by the effective density (i.e., the porosity) of the
Porous layer magnetite layer. Figure 15 shows the measured values compared
to the expected correlation for various presumed porosities of
C(Ldep) the deposit layer. The measured thickness is generally much
X
lower than expected from the measured loading, with potential
explanations for this discrepancy including that both measure-
ments cannot be applied at exactly the same location; the
thickness is effectively a single point measurement while the
loading is an average from a much larger area, and the sample
preparation procedure for the cross-sectional thickness mea-
surements could potentially induce some compaction. For
magnetite deposits known as “CRUD” that are considered re-
sponsible for UDC in light water reactors, a wide range of
porosity values from 30% to 85%, with typical values stated as

592 JULY 2022 • Vol. 78 • Issue 7 CORROSIONJOURNAL.ORG

 SCIENCE SECTION

(a) 1×10
8
(b) 1×105
W = 2.0
I = 0.5
1×104
Ccov = var
1×107
Chloride Concentration Factor C(Ldep)/C(0) 1×103

1×102
1×106
0.5 0.6 0.7 0.8 0.9 1
Ccov
(c) 1×104
W = 2.0
1×105
I = var
Ccov = 0.8

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1×103

1×104

1×102
0.3 0.4 0.5 0.6 0.7 0.8
I
1×103
(d) 1×104

1×102 1×103
W = var
I = 0.5
Ccov = 0.8
1×102
1×101
2 4 6 8 10 12 1.4 1.6 1.8 2 2.2 2.4 2.6
14
D W

FIGURE 14. Sensitivity of the calculated chloride concentration factor to the values of: (a) α, (b) Ccov, (c) ϕ, and (d) τ, for water temperature of
285.58°C and at Q = 425 kW/m2, and deposit thickness D = 101 μm, which is representative of the stage 4 UDC condition.

200
65% to 85% have been reported.35 In comparison, for the
multilaminate scales generated by corrosion of steel in acid
us

Stage 1
180
ro
po

Stage 2 us chloride solutions, a Pilling Bedworth ratio (oxide volume to

ro
%

Stage 3 po metal volume) of 2.4, which corresponds to a porosity of 13%36 is

50

160 Stage 4 % us
40 ro more typical. For our samples, if we estimate a maximum
po
0% porosity of 30% then the shaded triangle in Figure 15 shows the
Pm)

140 3
us
ro
Deposit Thickness (P

po possible zone for the properties of these deposits. At the

0% s measured loading threshold of 50 mg/cm2, the potential deposit
120 2 rou
po
10
% thickness ranges from approximately 95 μm at zero porosity,
100 us up to approximately 140 μm at 30% porosity. Similarly, at the
oro
No
np measured thickness threshold of approximately 95 μm, the
80 potential deposit loading ranges between approximately
35 mg/cm2 and 50 mg/cm2.
60 The wick-boiling model enables computation of the
concentration factor for corrosive impurities. Hence, for any bulk
40 boiler water composition, for a specific heat flux and deposit
thickness, it is in principle possible to calculate the local pH that is
20 created beneath the deposit. The method we have developed
for such calculations is described in detail in Appendix B. In short,
0 we assume that the only significant species are chlorides (as
0 10 20 30 40 50 60
HCl) and ammonia (as NH3 and NH4OH). We then further simplify
Deposit Loading (mg/cm2) the calculations by taking the chlorides to be concentrated
FIGURE 15. Measured values of deposit thickness and deposit loading beneath the deposits as described by the wick-boiling model,
in comparison with the expected correlation for various assumed while the ammonia concentration is considered to remain
porosities of the deposit layer. The shaded triangle indicates a plausible equal to that in the bulk water. This is a compromise between
region for deposits at the transition from stage 3 to stage 4 UDC. allowing the ammonia to concentrate (as does the chloride) or

CORROSIONJOURNAL.ORG JULY 2022 • Vol. 78 • Issue 7 593

SCIENCE SECTION

to vaporize completely (which might be expected) and was found
to produce pH estimates close to those reported by EPRI for
selected bulk compositions and concentration factors.2,37 Using
this model, it is calculated that 1.16 ppm of NH3 is required to
achieve a room temperature pH of 9.4 in bulk boiler water with
a chloride content of 125 ppb. For an assumed deposit
porosity of 30% (i.e., Ф = 0.3), Figure 16 then shows the calculated
pH (at 286°C) beneath the porous deposit, as functions of the
various key variables. For deposit thickness <30 μm, the chloride
concentration factor under the deposits is not high and the
local pH remains within the range of 5.6 to 5.8, which is close to
the pH of the bulk water (5.8). However, as the deposit
thickness increases, the concentration factor continues to
increase. The transition from stage 3 to stage 4 UDC occurs
once the concentration factor exceeds approximately 1,000 and
low alloy steels in deoxygenated acid chloride solutions at
temperatures up to approximately 300°C, making bulk solu-
tions for corrosion tests that were considered representative of
the concentrated solutions that could be generated by local
boiling and concentration in crevices between steam generator
tubes and their support plate in pressurized water reactors.
At the time of their work, this problem was known as “denting
corrosion,” because thick corrosion products formed in this
crevice could exert a compressive force on the outside of the
tubes, leading to deformation. For mixed solutions of ferrous
and nickel chlorides at 300°C with approximately 0.1 M to
1 M chloride and a room temperature pH of approximately 3.5
to 4.5, they reported corrosion rates of approximately 5 mm/y
to 20 mm/y.36 Consequently, it seems reasonable to suggest
that corrosion rates of approximately 20 mm/y could also

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the pH falls below about 2.7 (compared to the neutral pH at
286°C, which is ∼5.7). The metal skin temperature is essentially
equal to the boiling point of water at the 75 bar operating
pressure and was hence approximately 286°C. Comparison with
the work of Robertson, et al.,36,38-39 enables an estimate of
the corrosion rates under such conditions. Robertson and
colleagues36,38-39 studied the corrosion of carbon steels and
have been reached by the samples analyzed in the pres-
ent work.
We conclude that, for the specific conditions experienced
by the samples analyzed in this work, there was a significant
increase in the probability of stage 4 UDC at locations where the
heat flux exceeded 350 kW/m2 and the deposits had reached
a loading of approximately 50 mg/cm2, corresponding to a

104
5
Cl– Concentration Factor

103
pH (at 285.5°C)

102
3

101 2

100 1
0 25 50 75 100 125 150 0 25 50 75 100 125 150
Pm)
Deposit Thickness (P Deposit Thickness (Pm)
(a) (b)

6 6

5 5
pH (at 285.5°C)
pH (at 285.5°C)

4 4

3 3
Stage 1
Stage 2
2 2 Stage 3
Stage 4
1 1
50 100 150 200 250 300 350 400 0 1 2 3 4
Heat Flux (kW/m2) UDC Stage
(c) (d)
FIGURE 16. (a) Calculated concentration factor as a function of measured deposit thickness: and calculated pH under the porous deposits
as a function of (b) deposit thickness, (c) heat flux, and (d) the stage of UDC.

594 JULY 2022 • Vol. 78 • Issue 7 CORROSIONJOURNAL.ORG

 SCIENCE SECTION

deposit thickness of approximately 95 μm. Although it is industry 125

practice for practical purposes to use deposit loading as the
key indicator of UDC risk, the underlying physical threshold must 115

Pm)
depend on a combination of the metal skin temperature, local

Deposit Thickness (P
pH, and the relative concentration of chlorides to less aggressive 105
anions, such as phosphate. These factors will all vary depending
on the specific design and operating characteristics for the steam 95 25% porosity and critical pH (at 285.6°C) of 2.1
system under consideration. The modeling in this paper sug-
gests that the transition to stage 4 UDC occurred as the chloride 85
concentration beneath the deposits exceeded about 80 ppm
and the local at-temperature pH fell below approximately 2.7. 75 30% porosity and
critical pH (at 285.6°C) of 2.7
Taking the pH at the identified transition as the definition of the
underlying “critical pH” value at a heat-flux of 350 kW/m2, 65
Figure 17(a) then shows the critical deposit thickness re- 0 100 200 300 400 500 600 700 800 900 1,000
quired to generate that local pH as a function of the bulk boiler BW Chloride Concentration (ppb)
water chloride concentration, for assumed porosity values of (a)

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25% and 30%. For the lower assumed porosity, the calculated 125
concentration factor at 95 μm deposit thickness is much

Deposit Thickness (Pm)

greater (∼3,000) and so the calculated pH at the transition from
stage 3 to stage 4 is correspondingly lower, about 2.1.
Although the lower porosity also increases the concentration
factor for a given thickness, the overall effect is that the
lower assumed porosity leads to a small increase (up to ∼5 μm)
in the deposit thickness required for the transition from
stage 3 to stage 4 UDC.
For an assumed porosity of 30%, Figure 17(b) then
shows the critical deposit thickness required to generate that
local pH as a function of the bulk boiler water chloride
concentration, for three different values of the bulk boiler water
pH. For practical purposes, the impact of variations in bulk pH
are smaller than those in chloride concentration; a pH change
from 10 to 9.4 produces only a ∼4 μm decrease in the critical
deposit thickness, while a chloride change from 100 ppb to
200 ppb causes a decrease of approximately 10 μm. Such
variations in operational conditions translate directly to varia-
tions in the risk of UDC initiation at any instant in time. In our
view, the critical deposit thickness is somewhat analogous to a
pitting potential in that UDC or pitting occurs rapidly when
some critical value is exceeded, and that critical value is a
function of many variables. To reliably establish the critical pH
and the impact of all significant variables would require both a
large number of ex-service samples and a detailed record of
their operational history, neither of which are easily obtained.
Consequently, one potential future approach40 is to define
the critical local chemistry more precisely using simulated
local chemistry solutions as demonstrated by Robertson,
et al.,36,38-39 while further developing and validating the wick-
boiling model, thus enabling production of model curves such
as those shown in Figure 17 for a wider variety of operational
conditions.
CONCLUSIONS
115
105 For BW pH (25°C) = 10.0
For BW pH (25°C) = 9.8
95
For BW pH (25°C) = 9.4
85
75
65
0 100 200 300 400 500 600 700 800 900 1,000
BW Chloride Concentration (ppb)
(b)
FIGURE 17. The critical deposit thickness required to generate the local
pH beneath the deposit that is required for the transition from stage 3
to stage 4 UDC,40 as a function of the bulk BW concentration: (a) for two
different values of the deposit porosity and (b) for an assumed porosity
of 30% and three different values of the bulk BW pH.
➣ Using a simple model for the wick-boiling process beneath
porous deposits, it is estimated that the transition to rapid UDC
occurred for these samples as the local chloride concentration
exceeded about 80 ppm and the local at-temperature pH fell
below ∼2.7.
ACKNOWLEDGMENTS
The project is made possible by the National Priorities Re-
search Program-Standard (NPRP-S) Tenth Cycle Grant No.
NPRP12S-0228-190182 from the Qatar National Research
Fund (a member of Qatar Foundation). We would also like to
acknowledge Dr. Ram Ratnakar (Shell Technology Center,
Houston) for his contributions to the development of the wick-
boiling model for this paper.

➣ An electrochemical method has been developed for in situ

measurement of the deposit loading on the waterside of ac-
cessible steam generator tubes, without the need for de-
structive removal of the tubes.
➣ Analysis of ex-service 1.0 Cr 0.5 Mo steel coils from a
steam generator operating at 75 bar(a) under an AVT treatment
regime (with bulk boiler water pH of approximately 9.4 and
125 ppb chloride) suggests the threshold for the onset of rapid
(stage 4) UDC was at a heat flux of 350 kW/m2, deposit loading
of approximately 50 mg/cm2 and deposit thickness of approxi-
mately 95 μm.
References
1. IAPWS TGD3-10, “Volatile Treatments for the Steam-Water
Circuits of Fossil and Combined Cycle/HRSG Power Plants”
(International Association for the Properties of Water and Steam,
2010), available online at http://www.iapws.org/.
2. EPRI TR-1021767, “Comprehensive Cycle Chemistry Guidelines
for Fossil Plants” (Palo Alto, CA: Electric Power Research Institute,
2011).
3. VGB-S-010-T-00 (formerly VGB-R 450 Le), “Guideline for Feed
Water, Boiler Water and Steam Quality for Power Plants/Industrial
Plants” (VGB PowerTech e.V., 2011).

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SCIENCE SECTION

4. R.B. Dooley, A. Bursik, Powerplant Chem. 12 (2010): p. 188-192.
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13. EPRI TR-102401, “Guidelines for Chemical Cleaning of Fossil-
Fueled Steam-Generating Equipment” (Palo Alto, CA: Electric
44. N.G. Lensky, Y. Dvorkin, V. Lyakhovsky, I. Gertman, I. Gavrieli, Water
Resources Res. 41, 12 (2005): p. W12418.
45. K.S. Pedersen, P.L. Christensen, J.A. Shaikh, Phase Behavior of
Petroleum Reservoir Fluids (Boca Raton, FL: CRC Press, Taylor &
Francis, 2014), p. 1-465.
46. A. Vignes, Ind. Eng. Chem. Fundam. 5, 2 (1966): p. 189-199.
47. R.R. Ratnakar, B. Dindoruk, SPE J. 20, 05 (2015): p. 1-167.
APPENDIX A
The general species balance (or mass conservation) for
a solute under nonreacting conditions in a porous medium is
given by41-43
∂ðϕCÞ
þ ∇ × ðuCÞ − ∇ × ðDe ∇CÞ = 0 (A1)
∂t

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Power Research Institute, 1993).
14. EPRI TR-1008082, “Guidelines for Controlling Flow-Accelerated where the three terms represent the accumulation, convection,
Corrosion in Fossil and Combined Cycle Plants” (Palo Alto, and diffusion, respectively. Here, C is the solute’s molar
CA: Electric Power Research Institute, 2005). concentration, ϕ is the porosity, u is the fluid velocity, and De is
15. Y. Asakura, M. Kikuchi, S. Uchida, H. Yusa, Nucl. Sci. Eng. 67, 1 the effective diffusivity in porous media. The continuity
(1978): p. 1-7. equation, i.e., the overall material balance for the mixture
16. Y. Asakura, M. Kikuchi, S. Uchida, H. Yusa, Nucl. Sci. Eng. 72, 1
(1979): p. 117-120. (solute + solvent) is given by41-43
17. N.A. Mankina, B.L. Kokotov, Teploenergetika 9 (1973): p. 15-17.
18. G.M. Kaluzhskaya, R.A. Meyer, N.A. Mankina, Elekt. Stantsii 9 ∂ðϕρf Þ
(1960): p. 6-10. þ ∇ × ðuρf Þ = 0 (A2)
∂t
19. N.A. Mankina, A.G. Tkachenko, L.G. Bubnovskaya, Teplonergetika 9
(1960): p. 30-34.
20. N.A. Mankina, Elekt. Stantsii 2 (1962): p. 13-16. where ρf is the mass-density of the fluid. At steady state
∂
21. M. Basset, J. McInerney, N. Arbeau, D.H. Lister, Can. J. Chem. Eng. (i.e., ∂t = 0), and assuming 1D flow in the x direction, Equation (A1)
78 (2000): p. 40-52. simplifies to:
22. D.H. Lister, F.C. Cussac, Heat Transfer Eng. 30, 10-11 (2009): p.
840-850.  
∂ ∂C
23. T.K. Margulova, A.A. Belyaev, Teploenergetika 9 (1964): p. 45-51. uC − De =0 (A3)
24. L.Y. Krasyakova, I.I. Belyakov, Teploenergetika 1 (1970): p. 28-32. ∂x ∂x
25. N.A. Mankina, Teploenergetika 12 (1958): p. 12-18.
26. C.W. Turner, AECL Nucl. Rev. 2, 1 (2013): p. 61-88. Similarly, Equation (A2) simplifies to
27. F. Bozzoli, L. Cattani, A. Mocerino, S. Rainieri, J. Phys. Conf. Ser. 745,
3 (2016): p. 032034.
28. J.S. Jayakumar, Helically Coiled Heat Exchangers, Heat Exchan- ∂
ðuρf Þ = 0 ⇒ uρf = total mass flux = constant (A4)
gers–Basics Design Applications, ed. J. Mitrovic (London, United ∂x
Kingdom: InTech Open, 2012), p. 311-342.
29. ASTM D3483-14, “Standard Test Methods for Accumulated
Deposition in a Steam Generator Tube” (West Conshohocken,
The constant in Equation (A4) can be obtained by de-
PA: ASTM International, 2014).
30. G.F.V. Voort, “Metallography and Microstructures,” ASM Handbook, termining mass flux at x = Ldep (i.e., at the tube/wall interface
vol. 9 (Novelty, OH: ASM International, 2004), p. 313-316. beneath the porous deposits of thickness Ldep) due to boiling,
31. CRIEPI , “Optimization of Chemical Cleaning Interval for Super- which is the ratio of net heat flux (CQcov ) to the enthalpy of
critical Boilers,” Central Research Institute of Electric Power In- vaporization (ΔHv). This expresses the fluid velocity as follows:
dustry, CRIEPI report no. E280003, 1981.
32. G.V. Vasilenko, G.P. Sutotskie, Thermal Eng. 36 (1989).
∂ Q
33. F. Gonzalez, P. Spekken, Nucl. J. Can. 1 (1986): p. 129-140. ðuρf Þ = 0 ⇒ u = (A5)
34. A. Koponen, M. Kataja, J. Timonen, Phys. Rev. E 54 (1996): ∂x Ccov ΔHv ρw,l
p. 406-410.
35. C. Pan, B.G. Jones, A.J. Machiels, Nucl. Eng. Des. 99 (1987): where Ccov is the coverage or the fraction of area available for
p. 317-327.
evaporation and ρw,l is the liquid water density at x = Ldep.
36. J. Robertson, J.E. Forest, Corr. Sci. 32, 5/6 (1991): p. 521-540.
37. EPRI TR-1019641, “Cycle Chemistry Instrumentation Validation: Assuming that density is practically the same along the axial
Relationships of Cycle Chemistry Parameters” (Palo Alto, CA: direction, velocity u is independent of x. Note that to solve for
Electric Power Research Institute, 2010). concentration profile from Equation (A3), two boundary condi-
38. J. Robertson, Corr. Sci. 29, 11/12 (1989): p. 1275-1291. tions are required. The first boundary condition is Dirichlet
39. J.E. Forrest, J. Robertson, Corr. Sci. 32, 5/6 (1991): type where concentration at x = 0 is specified, i.e.,
p. 541-561.
40. A. Thyagarajan, W. Hamer, J. Phophichitra, V. Valliappan, A.
Ramesh, P. Shenai, N. Laycock, Corros. Mater. Degrad. 2 (2021): @x = 0, C = Cð0Þ (A6)
p. 762-769.
41. R.B. Bird, W.E. Stewart, E.N. Lightfoot, Transport Phenomena
(New York, NY: John Wiley & Sons Inc., 1960), p. 1-780.
The second boundary condition can be expressed in
42. K. Vafai, Handbook of Porous Media, 2nd ed. (Boca Raton, FL: CRC terms of molar flux of the solute at the boiling surface, which can
Press, Taylor & Francis, 2005), p. 1-742. be expressed in terms of entrainment coefficient (εE) and
43. R.R. Ratnakar, N. Kalia, V. Balakotaiah, Chem. Eng. Sci. 90 (2013): Henry’s constant H (for volatile solutes). This boundary condition
p. 179-199. can be expressed as follows

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 SCIENCE SECTION

@x = Ldep , of vaporization is low to moderate, the steam may not have

∂C enough inertia to entrain water with it. In addition, because the
uC − De = net molar flux of solute salt concentration (dissolved in water) is very low, the molar flux of
∂x
= flux of solute due to entrainment solute due to entrainment and evaporation can be neglected. In
this case, Equation (A8A) can further be simplified as follows:
þ flux of solute evaporated
    ∂C
Q 1 Q uC − De =0
= × εE × × CðLdep Þ þ × HCðLdep Þ ∂x
Ccov ΔHv ρw,l Ccov ΔHv ρw,l
and the specific solution to it also simplifies to
(A7)  
CðLdep Þ Q τ
= exp Ldep (A11)
Cð0Þ Ccov ΔHv ρw ϕD
Note that the entrainment coefficient εE is defined as the
kg of water entrained in per kg of steam (i.e., water evaporated).
Thus, CcovQΔHv × εE represents the mass flux of entrained water
We note that when the above solution is used at high
while CcovQΔHv × εE × ρ1w,l represents the volumetric flux (velocity) of
temperatures and pressures, one needs to know the
entrained water. Because the concentration of solute in the

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temperature-dependent values of the molecular diffusivity D. It
entrained water is the same as that at the boiling surface, the
can be computed by using Stokes-Einstein relations,46-47
flux due to entrainment is given by ðCcovQΔHv × εE × ρ1w,l × CðLdep ÞÞ.
Similarly, because Henry’s constant is defined as the ratio of T μ
D = DðTref Þ × × ref (A12)
concentration in the liquid to vapor phase, HC(Ldep) represents Tref μ
the concentration of solute in the vapor phase, and hence the
where D (Tref) and μref are the known diffusivity and the
term ðCcov ΔH
Q
v ρw,l
Þ × HCðLdep Þ represents the flux of solute
viscosity at a reference temperature Tref.
evaporating.
Thus, Equations (A3), (A5), and (A7) lead to
APPENDIX B
∂C The wick-boiling model allows one to compute the con-
uC − De = constant = uðεE þ HÞCðLdep Þ (A8A)
∂x centration factor for corrosive impurities like chlorides under the
deposits. Subsequently, estimation of local pH can help in
For low vaporization rate, the effective diffusivity (or assessing how corrosive the conditions become near the metal
dispersion coefficient) of a solute in porous media can be given wall, under the deposits, despite the bulk boiler water condi-
by VGB PowerTech e.V., [2011] as De = ϕD τ , where ϕ, τ, and D tions remaining fairly benign. Typically, the pH (25˚C) of boiler
are porosity, tortuosity, and the molecular diffusivity of the solute water is maintained above 9.0 via AVT. Ammonia as well as
respectively. Substituting the expressions for velocity u and amines are commonly used to implement AVT. The boiler water
the effective diffusivity De in Equation (A8A), we obtain the contains trace levels of chlorides (on the order of ppb). For a
following equation when the volatility of solutes dissolved in given concentration of chlorides in the boiler water, the required
water and water entrainment is important: dosage of total ammonia depends upon the target pH.
We assume the boiler water chemistry to be affected by
Q φD ∂C Q two species—chlorides and ammonia. In order to compute the
C− = ðε þ HÞCðLdep Þ (A8B)
Ccov ΔHv ρw,l τ ∂x Ccov ΔHv ρw,l E pH, one needs to consider the self-ionization equilibrium of
water, the ionic equilibrium of ammonia in water while simulta-
The specific solution to the above differential equation neously obeying the charge neutrality constraint. The ionic
can be obtained by using the boundary condition of equilibrium of ammonia in water NH3 þ H2 O ↔ NHþ −
4 þ OH is
Equation (A6) as characterized by the base dissociation constant kb as follows
 
CðxÞ − ðεE þ HÞCðLdep Þ Q τ ½NHþ −
4 ½OH 
ln = × ×x (A9) kb = (B1)
Cð0Þ − ðεE þ HÞCðLdep Þ Ccov ΔHv ρw,l φD ½NH3 

For a deposit of thickness Ldep (i.e., x = Ldep), exponen- The ionic product of water is given as
tiating both the sides and rearranging terms, we obtain the con-
centration factor for solutes under the deposit, i.e., the ratio of kw = ½Hþ ½OH−  (B2)
concentration near the boiling surface to that in the bulk water

CðLdep Þ 1 The charge-neutrality constraint implies

= τ
Cð0Þ ðH þ εE Þ þ ð1 − ðH þ εE ÞÞ exp½− φD Q
× Ccov ΔHv ρw,l
Ldep 
½Hþ  þ ½NHþ − −
4  = ½OH  þ ½Cl  (B3)
(A10)
Let A= total concentration of ammonia ([NH4+]+[NH3]), C =
It is interesting to note that most salts are nonvolatile when
[Cl−] and x = [OH−]. Substituting these terms in Equation (B1), we
dissolved in the liquid phase (sublimation temperature of salts are
obtain
usually very high as compared to the boiling point of liquids),
and hence Henry’s constants for salts are practically zero. ðC þ x − kxw Þx
Therefore, it is assumed in the literature that evaporation of kb =
A − ðC þ x − kxw Þ
brine (water + salt) leads to precipitation of salts and vapor
contains only water (without salt).44-45 Similarly, when the speed

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SCIENCE SECTION

Rearranging the terms, 6.5

pH (at 300°C) of BWC1
pH (at 300°C) of BWC2
6
x3 þ ðC þ kb Þx2 þ ðCkb − kw − kb AÞx − kw kb = 0 (B4)
5.5
Solving Equation (B4) for a real positive root yields [OH–].

pH (at 300°C)
While exact solutions for the cubic polynomial roots are known, 5
they are complicated. It is far simpler to solve for x graphically
or numerically and locate the root in the [10−14,1] domain cor- 4.5
responding to pOH= [14,1]. To ensure the accuracy of this
approach, we have first computed pH (at 25°C) and pH (at 300°C) 4
for two different boiler water compositions (BWC 1 and 2,
3.5
Table 3) provided in the EPRI Cycle Chemistry Guidelines report.2
Temperature-dependent values of kb and kw were obtained
3
from literature and using linear interpolation when required.37
Table 3 shows that the computed pH is consistent with the 2.5

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data from EPRI report. Note that for BWC2 where the water
contains Na+, in addition to NH3 and Cl–, the system can still be
reduced to effectively two ionic species (NH4+ and Cl−) apart from
H+ and OH− due to strong acid-base neutralization between
HCl and NaOH. The effective [Cl–] that influences pH in this case
is thus C= [Cl−]-[Na+].
The EPRI report also provides estimated pH for local
conditions representative of those under porous deposits ac-
counting for impurity concentrations due to the wick boiling
mechanism. The estimated pH for 1,000× concentration of BWC1
and BWC2 is 3.7 and 4.8, respectively. The specific consid-
erations on ammonia concentration and/or vapor-liquid equilib-
rium are unavailable. Using the approach outlined above, we
performed a sensitivity analysis as a function of ammonia con-
centration factor (relative to bulk water) while keeping the
concentration factor for chloride constant at 1,000×. As shown in
Figure B1, if one assumes ammonia to also concentrate by a
0 200 400 600 800 1,000
Concentration Factor For Total Ammonia Relative To Bulk Water
FIGURE B1. Computed pH at 300°C as a function of concentration
factor for ammonia—the ratio of concentration under the deposits to
that in the bulk water, for two different boiler water compositions.
factor of 1,000, the computed at temperature pH for BWC1 is
slightly acidic whereas that for BWC2 is alkaline. On the other
extreme, assuming vaporization of all of the ammonia leads to
highly acidic conditions under the deposits. We find that over a
range of 50× to 80× concentration factor for ammonia, minimum
deviation from the previous literature is observed. Liquid-
vapor partitioning of ammonia at a higher temperature along with
some concentration factor is required for accurate calculation
of pH.

598 JULY 2022 • Vol. 78 • Issue 7 CORROSIONJOURNAL.ORG

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