CORROSION ENGINEERING SECTION
Corrosion Control of Type 316L Stainless Steel
in Sulfamic Acid Cleaning Solutions
J.R. Kish,,* N.J. Stead,* and D.L. Singbeil*
ABSTRACT
An investigation was conducted to better understand the cor-
rosion behavior of Type 316L (UNS S31603) stainless steel in
sulfamic acid (NH2HSO3) cleaning solutions and the relative
merits of traditional corrosion control strategies. Gravimetric
and electrochemical measurements in deaerated and unin-
hibited 10 wt% NH2HSO3 at 65C revealed that corrosion pro-
ceeds in an active state and involves hydrogen evolution as
the dominant cathodic process. Effective corrosion control
attained through passivity can be attained through either
anodic polarization or the addition of a chemical passivator
(dissolved oxygen in this case). Upgrading to the more corro-
sion-resistant Type 2205 duplex stainless steel (UNS S32205)
was not considered reliable because this alloy exhibited bor-
derline passivity. Electrochemical and x-ray photoelectron
spectroscopy (XPS) surface microanalytical measurements
revealed that the effective corrosion control attained through
the addition of a commercial diethylthiourea-containing
organic inhibitor was related to the manner in which the
absorbed diethylthiourea inhibits the hydrogen evolution reac-
tion kinetics.
KEY WORDS: acid inhibitors, corrosion, corrosion resistance,
polarization, stainless steel, sulfamic acid
Submitted for publication June 2008; in revised form, February
2009.
Corresponding author. E-mail: kishjr@mcmaster.ca.
* FPInnovations Paprican, 3800 Wesbrook Mall, Vancouver, BC,
V6S 2L9 Canada.
(1) UNS numbers are listed in Metals and Alloys in the Unified Num-
bering System, published by the Society of Automotive Engineers
(SAE International) and cosponsored by ASTM International.
ISSN 0010-9312 (print), 1938-159X (online)
CORROSIONVol. 65, No. 7 09/000085/$5.00+$0.50/0 2009, NACE International
INTRODUCTION
Acid cleaning of equipment utilized in a chemi-
cal (kraft) pulp mill is required on a regular basis to
remove calcium carbonate-rich scale deposits. Such
scales need to be removed to maintain throughput
(digesters and pressure filters) and/or to maintain
heat transfer (evaporators and liquor heaters). Typi-
cal acids utilized for this purpose include hydrochlo-
ric acid (HCl), sulfamic acid (NH2HSO3), and formic
acid (HCOOH) for equipment fabricated from carbon
steel, and NH2HSO3, HCOOH, and nitric acid (HNO3)
for equipment fabricated from stainless steel. In most
cases, these acids should be used with an appropri-
ate corrosion inhibitor. The choice of acid solution
depends on a number of factors, which include, but
are not limited to, cost, cleaning efficiency, availabil-
ity, handling, storage, disposal, toxicity, and corro-
siveness.
Recently, a leak failure occurred in a NH2HSO3
cleaning system installed in a Canadian pulp and
paper mill. The failure occurred in a flanged elbow
fabricated from Type 316L (UNS S31603)(1) stainless
steel, which was leaking acid from perforations formed
adjacent to a welded flange.1 Significant corrosion
was also observed on the inside walls of the NH2HSO3
storage tank. The mill uses uninhibited 10 wt%
NH2HSO3 at 65C to clean the lime mud pressure fil-
ters. A tell-tale feature was the presence of grooves in
heavily corroded areas, which suggests that corrosion
occurred in an active state with hydrogen gas (H2) evo-
lution as the dominant cathodic process involved and
the formation of a semi-protective salt film.
491
CORROSION ENGINEERING SECTION
A study was undertaken to better understand the
corrosion behavior of Type 316L stainless steel in the
NH2HSO3 cleaning solution, and the relative merits of
traditional corrosion control strategies. The primary
objectives were to:
conduct a literature review to better understand
the chemical stability of NH2HSO3, and how
that stability affects the resultant corrosion
resistance of stainless steel;
conduct lab-based gravimetric and electro-
chemical tests to confirm the suspected corro-
sion mechanism, and to generate data required
to help the mill assess an appropriate corrective
action (materials selection, anodic passivation,
or chemical inhibition).
This report documents the major findings of this
effort. Preliminary results have been published,1 some
of which are included in this paper for completeness.
LITERATURE REVIEW
A summary of the chemical stability of aqueous
NH2HSO3 solutions is described below, and is based
on published information.2-5 The acid is moderately
soluble in water (H2O), having a solubility of 18 wt%
at 20C, which increases to 27 wt% at 60C. In aque-
ous solutions, NH2HSO3 is highly ionized according to:
NH 2SO 3H (aq) = H +(aq) + NH 2SO 3-(aq)
The ionization constant for the reaction is 0.103 at
25C. Therefore, it is a weaker acid than HCl and
H2SO4, but is a stronger acid than phosphoric acid
(H3PO4).
The temperature dependence of ionization is
described by:
-log K = (3,792.8/T) - 24.122 + 0.041544T
where K is the ionization constant and T is abso-
lute temperature in Kelvin. Ionization increases as
the temperature increases above 25C and reaches
a maximum at about 29C. After which, it decreases
with a further increase in temperature. Therefore,
the pH of the aqueous acid solution is likely to drop
(becomes more acidic) as the temperature drops from
the cleaning temperature of 65C to room tempera-
ture. However, the change would be small considering
the relatively small change in the ionization constant.
Aqueous solutions of NH2HSO3 are quite stable at
room temperature. However, at higher temperatures,
acidic solutions hydrolyze to produce ammonium
hydrogen sulfate (NH4HSO4) according to:
NH 2SO 3H (aq) + H 2O (l) = NH + -
4 (aq) + HSO 4 (aq)
The reaction involves undissociated NH2HSO3 mole-
cules and is first-order kinetics under activation con-
492
trol. Considering that the hydrogen sulfate anion
(HSO4) (K = 0.0102 at 25C) is a weaker acid than
NH2HSO3, the pH rises during hydrolysis. The rate of
hydrolysis is a function of both temperature and pH,
whereby the rate increases with increasing tempera-
ture and decreasing pH.
The acid reacts readily with basic metal oxides,
hydroxides, and carbonates to yield the corresponding
sulfamate salts. However, in the presence of certain
oxidizers, NH2HSO3 reacts readily to yield H2SO4, H2O,
and nitrogen gas (N2). Such oxidizers include HNO3,
nitrous acid (HNO2), chlorine (Cl2), and chlorates
(ClO3). In contrast, other oxidizers such as chromic
acid (H2CrO4), permanganic acid (HMnO4), and ferric
chloride (FeCl3) do not oxidize NH2HSO3.
Published corrosion data for stainless steel in
aqueous NH2HSO3 solutions, under typical acid
cleaning conditions, is quite limited. In one reported
study, the corrosion rate of Type 304 (UNS S30400)
stainless steel and Type 316 (UNS S31600) stainless
steel in uninhibited 10 wt% NH2HSO3 at 60C deter-
mined after 24 h exposure was less than 44 mpy
(1.1 mm/y) and less than 6 mpy (0.14 mm/y), respec-
tively.6 In that same study, the addition of a com-
mercial inhibitor (0.1 vol% to 0.3 vol%), and vigorous
stirring, increased the corrosion rate of Type 304
stainless steel up to 88 mpy (2.2 mm/y), whereas the
reported corrosion rate of Type 316 stainless steel
(1) remained unchanged. Based on these findings, it was
recommended that the inhibitor should be avoided
completely if cleaning stainless steel equipment.
That is a surprising recommendation considering the
rather large maximum corrosion rate reported for
Type 304 stainless steel after exposure to the unin-
hibited acid.
In a second reported study, gravimetric tests were
used to determine the corrosion rate of coupons made
(2) from Type 304L (UNS S30403) and Type 316L stain-
less steel in 10 wt% NH2HSO3 at 66C.7 Corrosion
rates tended to decrease with an increase in expo-
sure time. The stainless steel coupons exhibited some
minor crevice corrosion after exposure. The addition
of the same commercial inhibitor (0.2 vol%) used in
the other study was effective in reducing the corrosion
rates of the Type 304L and Type 316L stainless steel
coupons, as measured after 66 h of exposure.
In a more recent study, immersion tests were
used to document the corrosion rates of Type 304L
stainless steel coupons exposed to 20 wt% NH2HSO3
at 25C and 57C.8 In the uninhibited acid, the corro-
sion rate decreased with an increase in exposure time.
At 57C, the corrosion rate decreased from 3.6 mpy
(0.09 mm/y), after 4 h exposure, to about 1.2 mpy
(0.03 mm/y) after 24 h of exposure. The addition of
(3) the same commercial inhibitor (2.0 vol%) essentially
had no effect on the corrosion rate after 4 h of expo-
sure, whereas it had a minor beneficial effect after
24 h of exposure, regardless of the temperature.
CORROSIONJULY 2009
 CORROSION ENGINEERING SECTION

Table 1
Composition of Stainless Steels (wt%)
Type Form Heat C Si Mn P S Cr Ni Mo
304L Plate J4 0.016 0.48 1.64 0.031 0.014 18.07 9.92 N/A
Rod * N/A N/A 2.4 N/A N/A 17.9 8.8 0.44
316L Plate K7 0.018 0.55 1.52 0.033 0.001 17.1 11.2 2.09
Rod K10 0.016 0.31 1.42 0.024 0.001 16.8 11.2 2.06
2205 Plate AM2 0.030 0.48 1.44 0.020 0.001 22.0 5.7 3.01
Rod * N/A N/A 2.2 N/A N/A 21.3 6.0 3.0
N/A: not available; *: analyzed using Niton XLi 600 alloy (XRF) analyzer.

Based on the literature review, it is likely that the
corrosion of the flanged elbow and storage tank was
a result of exposure to the actual acid cleaning condi-
tions (uninhibited, 10 wt% NH2HSO3 at 65C), rather
than a result of a change in the acid chemistry with
time. From the temperature dependence of the ioniza-
tion constant, a decrease in temperature produces a
more acidic solution. However, the change in acidity
is likely too small to significantly affect the resultant
corrosivity. Besides, if the corrosion rate is under acti-
vation control, then the rate is expected to decrease
with a corresponding drop in temperature. Consid-
ering the products of hydrolysis (formation of HSO4),
the acid solution becomes less acidic with time. It is
assumed that the acid cleaning solution did not con-
tact any of the oxidizers that are capable of reacting
with NH2HSO3 to produce H2SO4. Unfortunately, little
can be inferred from the limited and conflicting cor-
rosion data for stainless steel in NH2HSO3 reported in
the literature.
EXPERIMENTAL procedures
Both gravimetric and electrochemical measure-
ments were made in the study. Rectangular test spec-
imens (15 cm2) were used in the gravimetric tests and
were prepared from commercial stainless steel plate,
provided in the mill-annealed condition. Cylindrical
test specimens (5 cm2) were used in the electrochemi-
cal tests and were prepared from commercial stainless
steel rod, provided in the mill-annealed condition.
Table 1 compares the chemical compositions of three
grades of the commercial stainless steel plate and rod
utilized. All samples were wet-ground to a 240-grit
surface finish using silicon carbide (SiC) paper,
cleaned in an aqueous soap solution, rinsed with eth-
anol (CH3CH2OH), dried using hot air, and weighed
prior to immersion. Upon removal, all samples were
cleaned in soap solution, rinsed with CH3CH2OH,
dried using hot air, and re-weighed.
Tests were conducted in synthetic 10 wt%
NH2HSO3 cleaning solutions prepared from reagent-
grade NH2HSO3 crystals and distilled and deion-
ized H2O. Solutions were contained in a conventional
1,000-mL electrochemical polarization test cell. The
cell was immersed in a H2O bath to maintain solu-
tion temperature at 65 1C. Deaerated and aer-
ated NH2HSO3 solutions were produced by bubbling
high-purity nitrogen (N2) gas and building air, respec-
tively, through the solution, for the entire duration
of the test using an immersed gas sparger. Inhibited
NH2HSO3 solutions were prepared by adding 0.1 vol%
of the same commercial inhibitor used in previously
reported studies.6-8 According to the MSDS (Material
Safety Data Sheet), this inhibitor is cationic and com-
prised of 30 wt% to 60 wt% alkyl pyridines, 10 wt%
to 30 wt% H2SO4, and 10 wt% to 30 wt% 1,3-diethyl-
thiourea. No attempt was made to mechanically agi-
tate the NH2HSO3 solutions.
Gravimetric tests involved exposing three sam-
ples of each grade of stainless steel to the synthetic
NH2HSO3 cleaning solution. Samples were suspended
in the solution using polytetrafluoroethylene (PTFE)
tape threaded through a 1/16-in-diameter hole drilled
into each. One sample was removed after three days,
a second sample after six days, and the third after
nine days.
Several electrochemical measurements were made
using stainless steel test electrodes, including cor-
rosion potential, linear polarization resistance, and
potentiodynamic anodic polarization. Cylindrical test
electrodes were mounted according to the ASTM G5
specification.9 Graphite rods were used as the coun-
ter electrodes. All potentials were measured against
an external silver/silver chloride (Ag/AgCl) reference
electrode, which was electrically connected to the test
solution using a Luggin salt bridge. The reference
potential of a Ag/AgCl electrode is 222 mV vs. the
standard hydrogen electrode (SHE). Liner polarization
measurements were performed according to the ASTM
G59 specification (scan rate of 10 mV/min),10 and the
potentiodynamic anodic polarization measurements
were conducted according to ASTM G5 specification
(scan rate of 10 mV/min).9
Complementary XPS measurements were made
on Type 316L cylindrical test electrodes immersed at
the naturally occurring corrosion potential in unin-
hibited and inhibited, deaerated 10 wt% NH2HSO3
at 65C for a period of 240 min. Reference measure-
ments were also made on an unexposed Type 316L
stainless steel electrode, a sample of reagent-grade
NH2HSO3 powder crystals, and a sample of reagent

CORROSIONVol. 65, No. 7 493

CORROSION ENGINEERING SECTION
(a)
Figure 1. (a) Plot of weight-loss measurements made on Type 316L stainless steel test coupons immersed in uninhibited
and inhibited, deaerated 10 wt% NH2HSO3 at 65C, as a function of time. (b) Expanded plot of weight loss as a function of
time for Type 316L stainless steel test coupons immersed in the inhibited acid solution.
Figure 2. Plot of inhibiting efficiency as a function of the inhibitor
concentration for Type 316L stainless steel. Inhibiting efficiency
calculated from a three-day weight-loss measurement in deaerated
10 wt% NH2HSO3 at 65C.
grade N,N-Di-n-butylthiourea powder crystals. All
measurements were carried out using a monochro-
mated Al K source. This technique was used to
characterize the composition of insoluble, adherent
surface compounds. The system collected the data
using a pass energy of 29.4 eV with a takeoff angle
of 75. Binding energies were referenced to the C 1s
peak at 285.0 eV.
RESULTS
Gravimetric Measurements
Figure 1 shows the results of the gravimetric
measurements made on the Type 316L stainless steel
samples immersed in deaerated 10 wt% NH2HSO3
at 65C. In the uninhibited acid, the weight loss
increased at a reasonably constant rate, as a function
494
(b)
of time. The obvious exception was the nine-day mea-
surement, which was somewhat higher than expected
from the linear corrosion kinetics. Weight-loss mea-
surements made on samples immersed in the inhib-
ited acid were significantly lower than they were in
the uninhibited acid, at all three exposure times con-
sidered. An expanded weight-loss scale (Figure 1[b])
shows that the weight loss measured in the inhibited
acid increased at a reasonably constant, yet decreased
rate after the three-day exposure. The annual corro-
sion rate for Type 316L stainless steel, extrapolated
from the nine-day weight-loss measurement, was
16 mpy (0.40 mm/y). The inhibiting efficiency was
88%, 92%, and 95% for the three-, six-, and nine-day
weight-loss measurement, respectively. The inhibit-
ing efficiency was calculated from the weight-loss data
using the expression:
wu - wi
efficiency (%) = w u # 100 (4)
where wu is the weight loss measured in the uninhib-
ited acid solution and wi is the weight loss measured
in the inhibited acid solution. These efficiencies indi-
cated that this commercial inhibitor had sufficient
persistence with respect to exposure time when added
at 0.1 vol%.
The influence of the inhibitor concentration on
the inhibiting efficiency for Type 316L stainless steel,
based on a three-day weight-loss measurement, is
plotted in Figure 2. Increasing the inhibitor concen-
tration from 1.14 104 g/L (0.01 vol%) to 1.14
103 g/L (0.1 vol%) increased the efficiency. However,
a further increase to 5.70 103 g/L (0.5 vol%)
decreased the efficiency. The inhibiting efficiency cal-
CORROSIONJULY 2009

(a)
FIGURE 3. Weight-loss measurements for Types 304L, 316L, and 2205 stainless steel samples immersed in deaerated,
uninhibited 10 wt% NH2HSO3 at 65C. (a) Plot of weight loss measured as function of time and (b) plot of average corrosion
rate calculated for the nine-day (216 h) weight-loss data point in (a). (1 mpy = 0.001 in/y = 0.025 mm/y).
culated from the data published by Crowe,7 which is
superimposed onto the plot, was consistent with the
trend toward decreased efficiency at inhibitor concen-
trations above 1.14 103 g/L (0.1 vol%).
Figure 3 shows the results of the gravimetric
measurements made on the three stainless steels
under study (Types 304L, 316L, and 2205) in deaer-
ated, uninhibited 10 wt% NH2HSO3 at 65C. The mea-
sured transient for the Types 304L and 316L stainless
steel samples showed the weight loss increased at a
reasonably constant rate. The rate associated with
the Type 316L stainless steel samples was signifi-
cantly lower than that for the Type 304L stainless
steel samples. The measured transient for the Type
2205 duplex stainless steel samples showed a com-
plex behavior, since there was no measurable weight
change on the six-day sample. If this data point was
excluded from the set, then the measured transient
would be similar to that derived from the Type 316L
stainless steel samples. Extrapolating the nine-day
weight-loss measurement to a corrosion rate for a
one-year period gave an annual corrosion rate of 70,
16, and 10 mpy (1.75, 0.40, and 0.25 mm/y) for the
Types 304L, 316L, and 2205 stainless steels, respec-
tively.
Electrochemical Measurements
Figure 4(a) plots the corrosion rate calculated
from the polarization resistance measurements made
on a Type 316L stainless steel electrode immersed in
deaerated 10 wt% NH2HSO3 at 65C, as a function
of time. The corrosion rate was calculated using an
anodic and cathodic Tafel slope of 100 mV/decade.
The purpose of this measurement was simply to
observe if there was any significant change in corro-
CORROSIONVol. 65, No. 7
CORROSION ENGINEERING SECTION
(b)
sion rate (passivation) during the exposure time. In
the uninhibited acid, the corrosion rate of the Type
316L stainless steel electrode decreased to a small
extent with increasing exposure time. However, this
decrease was not continuous. The maximum corro-
sion rate measured was 65 mpy (1.63 mm/y), whereas
the lowest rate measured was 32 mpy (0.80 mm/y). In
the inhibited acid, the measured corrosion rate was
significantly lower for the entire test. It decreased
monotonically with increasing exposure time. The
maximum corrosion rate measured, shortly after
immersion, was 6 mpy (0.15 mm/y), and the lowest
corrosion rate measured was 1.4 mpy (0.04 mm/y).
The inhibiting efficiency was 91% for the maximum
corrosion rate measured and 96% for the minimum
corrosion rate measured.
The corresponding corrosion potential transients
are plotted in Figure 4(b). In the uninhibited acid,
the corrosion potential showed much less variation
in time, as compared with the variation in the corro-
sion rate data. A minimum corrosion potential of
315 mVAg/AgCl was attained shortly after immersion.
Thereafter, the corrosion potential remained reason-
ably constant at 286 mVAg/AgCl. The corrosion poten-
tial measured in the inhibited acid was more negative
for the entire test. A minimum corrosion potential
of 372 mVAg/AgCl was attained after 89 h of exposure.
Thereafter, a steady-state corrosion potential of
320 mVAg/AgCl was established.
Figure 5 shows the influence of the inhibitor on
the potentiodynamic anodic polarization behavior of
a Type 316L electrode measured in deaerated 10 wt%
NH2HSO3 at 65C, after 30 min exposure. In both the
uninhibited and inhibited acid solutions, the polariza-
tion behavior exhibited classic active/passive behav-
495
CORROSION ENGINEERING SECTION
(a)
FIGURE 4. Open-circuit measurements made on a Type 316L stainless steel electrode immersed in deaerated 10 wt%
NH2HSO3 at 65C, as a function of time. (a) Plot of the corrosion rate calculated from the LPR measurements and (b) plot
of the corrosion potential measured during the same time period.
FIGURE 5. Influence of the inhibitor on the potentiodynamic anodic
polarization behavior of a Type 316L stainless steel electrode
immersed in deaerated 10 wt% NH2HSO3 at 65C, measured after
30 min of exposure.
ior, consisting of an active nose, followed by a state
of passive corrosion, then by a state of transpassive
corrosion. Cleary, the deaerated acid was not suffi-
ciently oxidizing to induce spontaneous passivation of
the Type 316L stainless steel electrode. Interestingly,
the inhibitor did not promote spontaneous passivation
either, yet it was effective in reducing the corrosion
rate by an order of magnitude.
The influence of aeration (dissolved oxygen) on
the potentiodynamic anodic polarization behavior of a
Type 316L electrode measured in uninhibited 10 wt%
NH2HSO3 at 65C, after 30 min exposure, is shown in
Figure 6. The corrosion potential was 191 mV more
positive in the aerated acid solution than it was in the
deaerated acid solution. Another marked feature was
the absence of an active-to-passive transition exhib-
ited by the electrode in the aerated acid solution.
Cleary, the aerated acid solution was sufficiently oxi-
496
(b)
dizing to induce spontaneous passivation. Aeration
had no influence on the passive state current density
or the transpassive potential.
Figure 7 compares the potentiodynamic anodic
polarization behavior of three stainless steels under
study, measured after 30 min exposure in deaerated,
uninhibited 10 wt% NH2HSO3 at 65C. The Type 304L
stainless steel electrode exhibited an anodic behav-
ior very similar to that exhibited by the Type 316L
stainless steel electrode. For both alloys, corrosion
spontaneously occurred in the active state, and an
active/passive transition occurred with mild anodic
polarization. The critical current for passivation was
somewhat smaller for the Type 304L stainless steel
electrode than it was for the Type 316L stainless
steel electrode. The anodic behavior of the Type 2205
duplex stainless steel electrode was significantly dif-
ferent than the other two. It did not exhibit a dis-
tinct active/passive transition. This behavior implied
that the Type 2205 duplex stainless steel electrode
was corroding in a passive state prior to the anodic
polarization experiment. Once passivated, all three
electrodes exhibited a similar passive state current
density and transpassive breakdown potential.
X-Ray Photoelectron Spectroscopy Surface
Measurements
Results for the S 2p, N 1s, O 1s, Fe 2p, Cr 2p,
and Ni 2p photoelectron spectra collected from the
surface of the three Type 316L stainless steel elec-
trodes and from the two powder samples analyzed
are compared in Figures 8 and 9. The powder sam-
ples were included to help differentiate between any
adsorbed electrolyte compounds (NH2HSO3/NH2SO3)
and/or any adsorbed inhibitor component on the
exposed Type 316L stainless steel electrodes.
CORROSIONJULY 2009
 CORROSION ENGINEERING SECTION

As the S 2p and N 1s spectra readily show, the

major core level binding energy of sulfur and nitro-
gen are distinctly different in the NH2HSO3 powder
than they were in the N,N-Di-n-butylthiourea powder.
The major S 2p and N 1s binding energy peaks were
169.7 eV and 401.7 eV, respectively, in the NH2HSO3
powder; they were 162.2 eV and 399.8 eV, respec-
tively, in the N,N-Di-n-butylthiourea powder. These
binding energy peaks are in good agreement with the
peak energies of 168.9 eV and 401.5 eV reported for
NH2HSO3,11 and with the peak energies of 162.2 eV
and 399.8 eV, respectively, reported for thiourea.12
Note that the inhibitor under study also contains a
FIGURE 6. Influence of dissolved oxygen (aeration) on the
mixture of alkyl pyridines, which were not analyzed by
potentiodynamic anodic polarization behavior of a Type 316L
XPS as part of this study. Consequently, the reported
stainless steel electrode immersed in uninhibited 10 wt% NH2HSO3
N 1s binding energy of 398.6 eV in pyridine13 was at 65C, measured after 30 min of exposure.
used to identify any adsorbed alkyl pyridine.
The data show that the unexposed Type 316L
stainless steel surface was covered by a relatively
thin mixed metal oxide film. The peak binding energies
of 711.4 eV (Fe 2p), 576.2 eV (Cr 2p), and 530.6 eV
(O 1s) are in good agreement with the values of these
core energies reported for Fe2O3 and Cr2O3.13 The
lower-energy shoulder in the Fe 2p spectrum was
consistent with a peak for metallic iron (706.7 eV),13
which indicates the presence of a reasonable thin
oxide layer. Note that there was little metallic or oxi-
dized nickel at the surface.
Upon exposure to the uninhibited 10 wt%
NH2HSO3 solution at the corrosion potential, the
binding energy peaks for oxidized chromium (Cr3+),
FIGURE 7. Plot comparing the potentiodynamic anodic polarization
oxidized iron (Fe3+), and metallic iron (Fe) were sig- behavior of Types 304L, 316L, and 2205 stainless steel electrodes
nificantly reduced on the Type 316L stainless steel immersed in deaerated, uninhibited 10 wt% NH2HSO3 at 65C,
surface. This reduction coincided with a reduction in measured after 30 min exposure.
the O 1s peak and a shift to a higher binding energy
(toward the peak corresponding to NH2HSO3). In addi-
tion, a small binding energy peak at 169.0 eV was the N,N-Di-n-butylthiourea powder. Regarding the
observed in the S 2p spectrum. Collectively, these N 1s spectrum, exposure to the inhibited 10 wt%
peaks indicate that the surface likely consisted chiefly NH2HSO3 solution increased and broadened (toward
of a thin mixed metal sulfamate corrosion product. higher binding energies) the peak and lower-energy
Note that this exposure increased, broadened, and shoulder observed after exposure to the uninhibited
shifted the N 1s binding energy peak toward a lower solution.
binding energy (away from the peak corresponding to
NH2HSO3). DISCUSSION
The binding energy peaks for oxidized chromium,
oxidized iron, and metallic iron were reduced fur- Corrosion Behavior
ther at the Type 316L stainless steel surface, after The corrosion and electrochemical testing con-
exposure to the inhibited 10 wt% NH2HSO3 solution. ducted confirmed that Type 316L stainless steel cor-
Again, this reduction coincided with a further reduc- rodes in an active state in the acid cleaning condition
tion and a further shift in the O 1s peak to a higher under study (deaerated, uninhibited 10 wt% NH2HSO3
binding energy. A more striking finding was the pres- at 65C), and involves hydrogen evolution as the dom-
ence of the binding energy peak of 856.2 eV and a inant cathodic process. The active corrosion state was
lower-energy shoulder in the Ni 2p spectrum. The confirmed by the anodic polarization behavior, which
position of the peak and the lower-energy shoulder showed that passivation was not spontaneous, since
is in good agreement with oxidized (Ni2+) and metallic the corrosion potential was more negative than the
nickel, respectively.13 Also of significance were the primary passivation potential. It was also confirmed
two peaks observed in the S 2s spectrum, which by relatively high corrosion rate data, as determined
occurred at the same energies as those observed in by the gravimetric test, as well as the long-term LPR

CORROSIONVol. 65, No. 7 497

CORROSION ENGINEERING SECTION

Reference Samples Type 316L Test Samples

S 2p

(a) (b)
N 1s
Counts [N(E)]

(c) (d)
O 1s

Binding Energy (keV)

(e) (g)
FIGURE 8. Photoelectron spectra for the major film-forming solution elements (S 2p, N 1s, and O 1s) collected from the
surface of the Type 316L stainless steel electrodes (unexposed, uninhibited, and inhibited), and from the two powder
reference samples analyzed (sulfamic acid and butlythiourea).

test. It is noted that the LPR corrosion rates were
calculated using default values (100 mV/decade) for
the anodic and cathodic Tafel slopes. Such practice
may induce an error as large as a factor of two.14
With this in mind, the instantaneous rate of 35 mpy
(0.88 mm/y) measured after the nine-day exposure
(216 h) may have been as high as 70 mpy (1.66 mm/y),
or as low as 18 mpy (0.44 mm/y). The low end of the
uncertainty range correlated reasonably well with the
time average rate of 16 mpy (0.40 mm/y) calculated
from the immersion test.
A cathodic reaction involving the evolution of
hydrogen gas was confirmed by the corrosion poten-
tial transient, which showed that the corrosion poten-
tial was more negative than the expected redox poten-
tial of the hydrogen evolution reaction of 261 mVAg/AgCl
for the entire immersion period. The expected redox
potential was estimated using the Nernst equation
with a hydrogen ion concentration of 0.275 mol/L,
which was calculated using the equilibrium defined
by Equation (1), and the temperature dependence
of the ionization constant defined in Equation (2).
Hydrogen evolution was also qualitatively confirmed
by the visual observation of gas bubbles forming on
the surface of the electrode during the immersion
period.

498 CORROSIONJULY 2009

 CORROSION ENGINEERING SECTION

Corrosion Control
Three corrosion control strategies were analyzed
in this study, namely, the addition of a commercial
inhibitor, the addition of a chemical passivator (dis-
solved oxygen through aeration), and the use of a
more corrosion-resistant stainless steel. Of these, the
first two were found to be effective. In contrast, the
third, selecting Type 2205 duplex stainless steel in
place of Type 316L stainless steel, was found to be
unreliable, since this stainless steel exhibited active-
passive behavior in the acid cleaning solution (deaer-
ated 10 wt% NH2HSO3 at 65C).
The addition of the commercial inhibitor was very
effective in controlling corrosion, since it reduced the (a)
corrosion rate of Type 316L stainless steel by an order
of magnitude. Given that the addition of this inhibitor
coincided with a shift in the corrosion potential in the
negative direction (Figure 4[b]) and a reduction in the
cathodic current density for all cathodic polarization
potentials (Figure 5), it is clear that inhibitor acted
primarily as a cathodic inhibitor. The similar cathodic
Tafel slope of 89 mV/decade and 83 mV/decade
extracted from the cathodic polarization curve in the
uninhibited and inhibited acid solutions, respectively
(Figure 5), suggests a simple blocking of the active
sites for hydrogen evolution by inhibitor compounds.
A simple check of the cathodic inhibiting efficiency,
calculated using the measured cathodic current den-
sity at a potential of 500 mVAg/AgCl and an equation (b)
similar to Equation (4), yields a value of 78%. This
efficiency, which was calculated using data obtained
in a potentiodynamic polarization experiment, cor-
relates reasonably well with the 88% efficiency,
which was calculated using data from a three-day
gravimetric experiment, providing further support of
a cathodic reaction inhibition mechanism.
As mentioned earlier, the commercial inhibitor
is comprised of 30 wt% to 60 wt% alkyl pyridines,
10 wt% to 30 wt% H2SO4, and 10 wt% to 30 wt%
1,3-diethylthiourea. The XPS results suggest that,
of the two major inhibiting components, the sulfur-
containing 1,3-diethylthiourea is playing a more
active role in inhibiting corrosion than the nitrogen-
containing alkyl pyridines. This finding is consistent (c)
with reports that show that sulfur-containing organic
FIGURE 9. Photoelectron spectra for the major film-forming alloying
inhibitors are generally more effective for steels in sul-
elements (Fe 2p, Cr 2p, and Ni 2p) collected from the surface of the
fur oxoacid solutions.15-17 It is also consistent with the Type 316L stainless steel electrodes (unexposed, uninhibited, and
well-known ability of thiourea to act predominantly as inhibited).
a cathodic inhibitor.18-19
Aerating the NH2HSO3 solution also proved effec-
tive in controlling corrosion of Type 316L stainless responds to a corrosion rate of 0.7 mpy (0.018 mm/y).
steel, since spontaneous passivation occurred upon Therefore, anodic passivation can reduce the active-
immersion. In this case the saturated dissolved oxy- state corrosion rate by a factor of about 20. A cathodic
gen content in the acid solution was sufficient to sup- potentiodynamic polarization curve measured using
ply a cathodic current in excess of the critical current a platinum electrode in aerated 10 wt% NH2HSO3 at
required for passivity at the passivation potential. The 65C exhibited the expected behavior consisting of
passive state current density of 1.727 103 mA/cm2 a mass-transport-controlled limiting current at low
measured at an anodic potential of 300 mVAg/AgCl cor- overpotentials (oxygen reduction reaction) and a Tafel

CORROSIONVol. 65, No. 7 499

CORROSION ENGINEERING SECTION
current at high overpotentials (hydrogen evolution
reaction). Consequently, any attempt at using aera-
tion as a corrosion control strategy may have addi-
tional solution movement issues to overcome.
Of the three stainless steels studied, Type 2205
duplex stainless steel exhibited the highest corrosion
resistance to deaerated 10 wt% NH2HSO3 at 65C.
However, it appears as though Type 2205 duplex
stainless steel exhibits active/passive behavior in this
environment. In the corrosion test, the three-day and
the nine-day weight loss exhibited by this stainless
steel was marginally lower than that exhibited by Type
316L stainless steel, whereas the weight loss of the
six-day sample was significantly lower. Furthermore,
the Type 2205 duplex stainless steel electrode did not
exhibit an active-to-passive transition during anodic
polarization. If this duplex stainless steel can spon-
taneously passivate in deaerated 10 wt% NH2HSO3
at 65C, then it may be a more appropriate stain-
less steel from which to fabricate systems handling
uninhibited NH2HSO3 cleaning solutions. However,
the active corrosion behavior exhibited in part during
the corrosion test clearly shows the corrosion conse-
quences of unreliable passivation.
CONCLUSIONS
v Gravimetric and electrochemical testing confirmed
that Type 316L stainless steel corrodes in an active
state in deaerated, uninhibited 10 wt% NH2HSO3 at
65C (the acid cleaning solution under study), and
involves hydrogen evolution as the dominant cathodic
process.
v The addition of the diethylthiourea-containing
commercial inhibitor was very effective in control-
ling corrosion, since it reduced the corrosion rate
of Type 316L stainless steel by an order of magni-
tude. Effective corrosion control is related in a man-
ner in which the absorbed diethylthiourea inhibits the
hydrogen evolution reaction kinetics.
v Aerating the 10 wt% NH2HSO3 solution at 65C
also proved effective in controlling corrosion of Type
316L stainless steel, since spontaneous passivation
occurred upon immersion. Anodic passivation can
reduce the active-state corrosion rate by a factor of
about 20.
v Of the three stainless steels studied, Type 2205
duplex stainless steel exhibited the relative highest
500
corrosion resistance to deaerated, uninhibited 10 wt%
NH2HSO3 at 65C. However, the use of Type 2205
duplex stainless steel to contain this environment is
not considered reliable, since this alloy exhibited bor-
derline passivity.
ACKNOWLEDGMENTS
The technical information and assistance pro-
vided by Member Company mill personnel and Craig
Reid (ACUREN Group Inc.) is greatly appreciated.
Thanks to K. Tanner (undergraduate student) for con-
ducting the gravimetric testing.
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