P R E P R I N T – ICPWS XV

Berlin, September 8–11, 2008

Effect of Water Chemistry on Deposition Rate of Iron Corrosion Products in Boiler

Tubes

Tamara I. Petrovaa, Valery I. Kashinskya, Anastasia G. Isianovaa, R. Barry Dooleyb

(Moscow Power Engineering Institute, Russia)a, (Structural Integrity Associates, Canada)b

Email: petrova@twt.mpei..ac.ru

The experimental date were given of influence different types of water chemistry (AVT, OT,
RT) on deposition rate iron corrosion products on the surface of carbon steel in watper at
temperature nearly 350°. It was installed, that minimal deposition rate was observed for OT at
heat flux from 0 to 300 kW/m2. There are many mathematical models given in literature that
account for different deposition factors, but there is almost no information on estimation of the
effect of individual factors and highlight the major ones. Analysis of influence of different
parameters on deposition rate of corrosion products based on MEI test data was performed. The
deposition equation that let’s to predict the process of deposition rate with account the time of
fluid contact with surface was suggested.

Reliability of operation of heating surfaces of
modern boilers is determined mostly by deposition
rate on heat exchange surfaces. Numerous
laboratory and field test results have shown that
deposits are distributed non-uniformly along the
height of waterwalls: the predominant amount of
deposits is in high flux zones.
In spite of more rigid requirements towards
feedwater purity, the deposition rate on heat
exchange surfaces in boilers has increased in going
to higher operational parameters. This results in
decrease in operational period between cleanings
and increase in the risk of equipment failures.
Due to increased feedwater purity in sub-critical
and supercritical boilers, the deposits on steam
generation surfaces mostly consist of corrosion
products of construction materials, i.e. iron and
copper oxides. Since forms of existence of iron and
copper corrosion products depend on water
chemistry, the deposition rate of the above-
mentioned impurities would depend on the type of
water chemistry. Therefore, optimization of water
chemistry is an important practical issue, in
particular for the power plants with mixed
metallurgy.
For prediction of formation of deposits on boiler
tube surfaces it is necessary first of all to have
physical model that would account for the
maximum number of deposition-influencing factors.
From the physical model, mathematical deposition
model could be developed.
There are many mathematical models given in
literature that account for different deposition
factors, but there is almost no information on
estimation of the effect of individual factors and
highlight the major ones.
The basic aim of this work was to analyze
existing mathematical models and to estimate the
effect of individual factors on deposition based on
MEI test data.
Laboratory and field data show that properties
and composition of iron oxides in boiler water
depend on water chemistry [1, 2]. The most popular
water treatment scheme for drum-type boilers at
present is ammonia/hydrazine (or ammonia only)
feedwater treatment (AVT) and phosphate
treatment of boiler water (PT). At some fossil
plants with drum boilers oxygenated treatment (OT)
is employed. Comparison of composition of iron
corrosion deposits with AVT and OT shows that
with the former it is mostly Fe3O4, and with the
latter – Fe3O4, FeO, Fe2O3, and -Fe [2]. The form
of existence of iron corrosion products in water is
also different: with AVT it is in Fe3O4 form, and
with OT – in Fe(OH)3 form [1]. Different forms of
iron existence in water should make a difference in
the deposition rate on heat exchange surfaces.
The tests performed in Moscow Power Institute
(MEI) under agreement with EPRI [3, 4] showed
that the deposition rate depended on water
chemistry: at OT it was lower that with AVT, water
temperature, heat flux, and iron concentration being
the same
The test data produced at iron concentration of
10 ppm and the heat flux range of 50 – 300 kW/m2
have been used for generation of empirical
equations of deposition rate of iron corrosion
products:
 AVT: А1 = К1 · CFe · q2.3 + В1, (1)

OT: А2 = К2 · CFe · q1.9 + В2, (2)

where A1 and A2 are the deposition rates at

AVT and OT, respectively, mg/(cm2 · h); K1 and K2
are the proportion coefficients at AVT and OT,
respectively; CFe is the iron content in water, ppb; q
is the heat flux, kW/m2; B1 and B2 are the constants
at AVT and OT, respectively.
Figure 1: Deposition Rate of Iron Corrosion
The values of proportion coefficients and
Products vs. Heat Flux (CFe = 40 ppb, AVT):
constants are as follows:
1 – calculated with Equation (1); 2 – calculated
К1 = 5.843 · 10-6; К2 = 3.335 · 10-5
with equation (2); 3 – test data [3, 4].

В1 = 5.52 · 10-7; В2 = 2.21 · 10-3

It is evident that heat flux with OT is somewhat

lower that with AVT. Coefficient K2 and constant
B2 are also lower with OT.
These equations were used for calculation of the
deposition rate at the concentration of iron
corrosion products in water of 40 ppb; also
equations (1) and (2) were used. The results are
shown in Figures 1 and 2. There is pretty good
agreement between calculation and experiment over
Figure 2: Deposition Rate of Iron Corrosion
the heat flux range of 50 – 150 kW/m2. At higher
Products vs. Heat Flux (CFe = 40 ppb, OT):
heat flux (up to 300 kW/m2) there is difference
1 – calculated with Equation (1); 2 – calculated
between calculation and experiment, and this
with equation (2); 3 – test data [3, 4].
difference is less pronounced if to use the equation
(2) with subtraction of soluble iron from total iron
The value of pH when the charge of colloidal
concentration at the given temperature.
particle is zero is called the isoelectric pH, or pHiso.
Concentration of iron corrosion products in
At temperature 25 oC for the majority of colloidal
boiler water, as a rule, exceeds iron solubility.
particles this value is about 7: pHiso for Fe3O4 is
These products may have different size and carry
6.5±0.2, for α-Fe2O3 – 6.7, for γ-Fe2O3 – 6.7±0.2,
electric charge. In this case deposition mechanism
for α-FeOOH – 6.7±0.2. For Fe(OH)2 and Fe(OH)3
may be explained by particle charge due to both ion
these values are higher – 12±0.5 and 8.5
adsorption ability from water and transport of
respectively. At elevated temperatures (ca. 200 °C)
hydroxyl-ions from particle surface layer to water.
pHiso of iron corrosion products is close to 7 [7].
Deposition of iron corrosion products may be
Particles of the majority of forms of iron
controlled by recharging of corrosion particles [5,
corrosion products at pH of 5-12 have positive
6]. Change of charge sign can be achieved, in turn,
charge, and at higher pH values – negative charge.
either by change in pH of fluid or by feed of alien
Due to the change of the charge polarity at pretty
ions with opposite charge capable for selective
high alkalinity it could had been assumed that with
sorption on the surface of corrosion particles.
variation of pH value it would be possible to almost
Polarity and magnitude of iron corrosion
eliminate the deposition of iron corrosion products.
particle charge is given by both molecular and fluid
This was proved experimentally (Figure 3) [8]. By
properties with predominant influence of potential-
keeping solution pH higher than 12, it could be
forming ions, among other factors. For example, at
possible to prevent almost completely the iron
chemistry with no additions of conditioning
oxide deposition. Although this conclusion is of no
chemicals, these potential-forming ions for iron
practical value, nevertheless it confirms validity of
oxides are either OH- or H+. This is why charge of
the above-mentioned idea on the mechanism of iron
iron corrosion products depends on fluid pH.
oxide deposition. Therefore, development of
mathematical models should consider, in addition

2
to heat flux and concentration of iron corrosion
products, electrophoretic properties of corrosion
particles.
Figure 3: Effect of Fluid pH on Amount of Iron
Deposits.
In addition, large number of other iron
deposition-influencing factors is considered in the
literature. Among these: flow velocity; temperature
of flow and wall; fluid type (single- or two-phase);
amount, composition, porosity, and thermal
conductivity of deposits; surface finish; uniformity
of surface heating; presence of electromagnetic
field; time of fluid contact with surface etc. The
general information on the well-known factors and
areas, where better understanding is needed, is
given in [9]. For development of mathematical
model it is necessary to separate basic parameters
that would influence deposition rate for that
specific operational case of equipment from total
number of parameters.
Generally, the physical model of the deposition
of iron corrosion products consists of the following
stages:
• Physical interaction of colloidal and
suspended particles with tube surface.
The process of corrosion particle
precipitation on the surface can be
arbitrarily split into two phases: delivery
phase and wall adhesion phase. During the
delivery phase of particles from flow
nucleus to the wall-adjacent zone,
hydrodynamic forces play a leading role.
During the wall adhesion phase, molecular
interaction forces play the leading role.
The particles can interact with either the
surface itself (if tube is clean) or with
previously deposited layer of particles.
Particle adhesion requires higher
magnitudes of adhesion and friction forces
compared to hydrodynamic and elastic
3
repulsion forces, otherwise particles will
be carried away from the surface with flow.
• Formation of solid phase from low-soluble
impurities present in water.
The solid phase formed in the bulk fluid
flow is deposited on the tube surface. As a
rule, this process occurs with change in
fluid temperature.
• Adsorption and ion exchange on the
surface of suspended particles and in pores
of existing deposits.
This stage includes sorption of impurities
dissolved in water on colloidal and coarse
particles present in water, as well as on the
surface and in the pores of deposits.
Therefore, during development of the
deposition model it is necessary to
consider maximum number of parameters
involved in each above-mentioned
deposition stage.
Literature references present numerous
dependencies that describe deposition of
construction materials on heat exchange surfaces.
Approach towards development of models and
estimation of the major deposition-influencing
parameters differs significantly in these
publications. For example, it is suggested that
electrostatic interaction between charged particle
and tube surface is the crucial factor for deposition
of iron corrosion products [10]. Author makes a
postulate that application of electric field causes
motion of charged particles.
The particle flow A towards the surface under
the electric field is:
А = U · CFe (3)
Thus, amount of formed deposits depends on
motion velocity of particles and concentration of
iron corrosion products. Mathematical treatment of
the equation (3) results in dependence on deposition
of iron corrosion products expressed with equation :
A = K C Fe q n (4)
It is stated that exponent (n) of the heat flux can
fluctuate from 1 to 3.5. This discrepancy is
explained in [11] by different ratio between the
surface charge of the particle; the effective
thickness of the double layer and the electric field
magnitude.
 Another model considers heat-and-mass transfer
that occur during motion of fluid with suspended
particles in heated tube [12]. The following
simplified equation is suggested for determination
of the deposition rate (A):
β ⋅q dv
А = 10 −3 ⋅ ⋅С ⋅( )⋅ p (5)
v w− a di w− a
where Vn/Vw-a is the ratio of specific volumes in the
flow nucleus and wall-adjacent zone; is the ratio
between outer and inner tube diameters; q is the
outer tube surface heat flux density; iw-a is the
enthalpy of the fluid in the wall-adjacent zone; C is
the concentration of iron corrosion products in the
fluid.
Glebov [12] assumes that equation (5) combines
together such important parameters like surface
density of heat flux, fluid condition, mass velocity,
concentration of suspended solids, i.e. factors that
directly govern processes occurring in the heated
tube. It should be noted that the pattern of equation
(5) is similar to that given by Zwickler [13]:
V0 1 dV
А = q ⋅ C0 ⋅ ⋅ ⋅ (6)
V V dt
The difference between equations (5) and (6) is
that equation (6) has additional ratio V0/V.
Comparison of two different approaches
towards compilation of mathematical equations on
deposition shows that in both cases the common
values are heat flux and concentration of corrosion
products. It is not so easy to estimate effect of other
parameters given in different equations.
On the basis of the MEI test data [3, 4], an
attempt has been made to estimate effect of each
monitored parameter on deposition rate of iron
corrosion products.
For this, a correlation-regression analysis test
data was performed with STATISTICA 7.0
software [14, 15] that consisted of a number of
modules for a certain group of analytical methods.
The results of this estimation are presented in Table
1. Here correlation and confidence coefficients for
each monitored test parameter are given. The closer
correlation coefficient to unity, the stronger
dependence between parameters. The lower
confidence coefficient, the higher confidence in
correlation coefficient [5, 16].

Table 1: Analysis of Effect of Different factors on Deposition of Iron Corrosion Products with OT and AVT

OT AVT
N
AFe · 10-2, mg / (cm2 · h) AFe · 10-2, mg / (cm2 · h)
o.
Parameter k (correlation coefficient) Parameter k (correlation coefficient)
р (confidence coefficient) р (confidence coefficient)
k = 0,9343 k = 0,7833
1 Q, kW/m2 Q, kW/m2
р = 0,0001 р = 0,001
k = 0,7753 k = 0,0001
2 twall, °C twall, °C
р = 0,003 р = 0,001
k = 0,0008 k = 0,0002
3 Time, h Time, h
р = 0,008 р = 0,010
k = 0,0003 k = 0,3476
4 twater, °C twater, °C
р = 0,015 р = 0,223
k = 0,0005 k = 0,2844
5 pH pH
р = 0,203 р = 0,324
k = 0,2529 k = 0,2738
6 ORP ORP
р = 0,428 р = 0,343
k = 0,2231 k = 0,2001
7 Fe, ppb Fe, ppb
р = 0,486 р = 0,493
k = 0,1542 k = 0,1667
8 Na, ppb Na, ppb
р = 0,632 р = 0,569
k = 0,1260 k = 0,0814
9 sc, μS/cm sc, μS/cm
р = 0,696 р = 0,782

4
 Comparison of the estimation data for AVT and
OT shows that heat flux has the highest impact on
the deposition rate of iron corrosion products.
Effect of other parameters is different at AVT and
OT. For example, at OT tube wall and water
temperatures are Nos. 2 and 3 respectively, and at
AVT these are: water temperature and test duration.
It should be noted that effect of iron corrosion
products at OT is No. 7, and at AVT – No. 5.
These results confirm once again need to
account during development of deposition models
for specific operational conditions of equipment.
In equation (4) the unit of the coefficient K
contains time in nominator. Apparently, if the
coefficient is determined this way, it cannot be
universal, because it characterizes specific test rig.
More correct way of the data processing for the
deposition rate would be as follows:
А = К’ · CFe · q · τ (7)
where K’ is the proportion coefficient; CFe is the
iron concentration in water, q is the specific heat
flux; τ is the time of exposure to heat flux.
This equation corresponds to the equation (8)
[17]:
dAi = – K · C · ( Σμin − ΣμiK ) ⋅ q ⋅ dτ
(8)
where ( Σμin − ΣμiK ) is the thermodynamic
parameter of the system.
In this case the coefficient K’ does not depend
on time and could be valid for other test rigs. It is
evident that the test data serving as a basis for the
equation (4) will have the fit by equation (7) with
the same accuracy. It is necessary only to determine
time of exposure of iron corrosion products to heat
flux for the conditions of the test data. Integration
of equation (8) should be performed from 0 to max,
since in this time range all the parameters in the
equation make sense.
Conclusions
1. Analysis of the major thermal and chemical
factors that influence on deposition rate of iron
corrosion products was performed.
2. Physical model of deposition on heat exchange
surfaces was considered.
3. Mathematical deposition equations were
described.
4. Analysis of influence of different parameters
on deposition rate of corrosion products based
on MEI test data was performed.
5
5. The deposition equation that accounts for the
time of fluid contact with surface was
suggested.
References
[1] G.V. Vasilenko, V.I. Zarembo “Chemistry
Water and Steam at Power Plants” St.
Petersburg. (2007).
[2] I.I. Chudnovskaya, “The Structure and Phase
Composition of Inner Deposits in Lower
Radiant Section Tubes,” Teploenergetika.
No. 11, pp. 68 – 70 (1979).
[3] Deposition on Drum Boiler Tube Surfaces,
EPRI, Palo Alto, CA: (2004) 1008083.
[4] Deposition on Drum Boiler Tube Surfaces,
EPRI, Palo Alto, CA (2005) 1010186.
[5] N.N. Mankina, M.M. Przhevalsky, Yu.I.
Bulavitsky, and I.N. Petrova, “Formation of
Iron Oxide Scale in Steam Boilers with
Multiple Circulation,” Teploenergetika. No.
2, pp. 79 – 83 (1959).
[6] V.P. Brusakov, “Regularities of Release of
Substances on Heat Exchange Surfaces
under Action of Thermoelectric
Phenomena,” Atomnaya Energiya. Vol. 30,
No. 1, pp. 10 – 14 (1971).
[7] O.I. Martynova, A.A. Gromoglasov, A.Yu.
Mikhailov, and M.L. Nasyrov, “The Study of
Temperature Effect on Electrophoretic
Mobility of Corrosion Products,”
Teploenergetika. No. 2, pp. 70 – 73 (1977).
[8] T.Kh. Margulova. Water Chemistry of Fossil
Power Plants. Energiya, Moscow -
Leningrad, USSR, (1965).
[9] W.E. Allmon, M.G. Pop, and K.J. Shields,
“Deposit Characteristics for Modeling
Deposition Processes in Fossil Boilers,”
Proceedings: Eighth International
Conference on Cycle Chemistry in Fossil
and Combined Cycle Plants with Heat
Recovery Steam Generators, June 20 - 22,
2006, Calgary, Alberta, Canada. EPRI, Palo
Alto, CA: (2007). 1014831.
[10] N.N. Mankina and B.L. Lokotov, “On the
Mechanism of Iron Oxide Scaling”,
Teploenergetika. No. 9, pp. 15 – 17 (1973).
[11] V.T. Levich. Physico-Chemical
Thermodynamics. AN SSSR, Moscow,
USSR, (1952).
[12] V.P. Glebov, “Analytical determination of
Amount of Iron Oxide Deposits on Inner
Tube Surface in Supercritical Boilers,
Teploenergetika. No. 3, pp. 55 – 58 (1979).
[13] R. Zwickler, “Der Einfluss poröser
Eisenoxidablage rungen auf der
Wärmeübergang bei überkritishen Drücken,
VGB Speisewasser tagung (1966).
[14] V.P. Borovikov. Popular Introduction in
STATISTICA Software. Computer Press,
Moscow, Russia, (1998).
[15] V.P. Borovikov. STATISTICA. Art of Data
Analysis with Computer. 2nd Edition. Piter,
S-Petersburg, Russia, (2003).
[16] M.A. Styrikovich, O.I. Martynova, and Z.L.
Miropolsky. Steam Generation at Power
Plants. Energiya, Moscow, USSR, (1969).
[17] N.I. Gruzdev, “On Some Features of BWR
Water Chemistry,” Teploenergetika. No. 1,
pp. 17 – 20 (1975).