Materials Letters 59 (2005) 570 – 574

www.elsevier.com/locate/matlet

Improved corrosion resistance of Ni–22Cr–13Mo–4W Alloy by surface

nanocrystallization
K.S. Raja*, S.A. Namjoshi, M. Misra
Metallurgical and Materials Engineering, University of Nevada, Reno, NV 89557, USA

Received 11 September 2004; accepted 22 October 2004

Available online 2 November 2004

Abstract

Surface modification treatments were carried out on Alloy 22, a nickel base Ni–22Cr–13Mo–4W alloy, using shot peening process
followed by low-temperature annealing. Electrochemical corrosion experiments were carried out on the surface modified specimens in hot
acid chloride solution. Passivation and Mott–Schottky (M–S) analysis were carried out in sulfuric acid solution at room temperature.
Improved passivity and better electronic properties of passive film were observed on the surface modified specimens that could be attributed
to the surface nanocrystallization.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Corrosion; Ni base alloy; Surface nanocrystallization; Passive film

1. Introduction
Alloy 22 (UNS N06022), a nickel base Ni–22Cr–13Mo–
4W alloy, shows excellent corrosion resistance in both
oxidizing and reducing environments [1]. It is a candidate
material for fabrication of the outer wall of nuclear waste
packages for the proposed Yucca Mountain Nuclear Waste
Repository in the USA. It is expected that the structural
integrity of the waste package containers should last longer
than 10,000 years. As environmental degradation is consid-
ered the most probable damaging mechanism, extensive
investigations are being carried out to predict long-term
corrosion behavior of the Alloy 22 and methods to improve
the corrosion resistance as well [1].
One of the methods of corrosion mitigation in nuclear
industries is application of insulator type ceramic coating on
the surface to be protected [2]. Recently, formation of
nanocrystalline surface is proposed for enhanced surface
properties [3–6]. Nanocrystallization of surface layer has
* Corresponding author. Tel.: +1 775 784 7789; fax: +1 775 327 5059.
E-mail address: ksraja@unr.edu (K.S. Raja).
0167-577X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2004.10.047
been carried out by processes such as shot peening [3,4] and
shot blasting and annealing [5,6]. Superior corrosion
properties of the nanocrystalline surfaces of 304 SS and
brass were observed by Li et al. [5,6]. The enhanced
electrochemical behavior of the nanocrystalline surface was
attributed to the increased density of diffusion paths
available for alloying elements migrate and rapidly form a
protective passive film [5]. In conventional stainless alloys
(with microns size grains), formation of nanometer scale
passive film imparts good corrosion resistance. Therefore, it
is logical to expect that surface nanocrystallization would
result in formation of the passive film with enhanced
electrochemical properties. However, the electrochemical
properties of the passive films formed on the nanocrystalline
surfaces have not been evaluated systematically in order to
understand the underlying mechanism of the observed
increase in corrosion resistance.
In this short communication, surface nanocrystallization
of Alloy 22 has been carried out using shot peening and low-
temperature annealing route, and semiconducting properties
of the passive film formed on the nanocrystalline surface
have been evaluated using Mott–Schottky (M–S) analyses.
The observed improvement in corrosion resistance of the
 K.S. Raja et al. / Materials Letters 59 (2005) 570–574
nanocrystalline surface has been correlated with the elec-
tronic properties of the passive film.
2. Experimental
The chemical composition of the material, Alloy 22
(UNS N06022), used in this investigation is 0.002% C,
0.03% Si, 0.002% S, b0.005% P, 0.24% Mn, 0.15% V, 1.3%
Co, 3.50% Fe, 2.8% W, 13.1% Mo, 21.7% Cr, and balance
Ni. Cylindrical specimens (11.3-mm diameter and 10-mm
thick) were machined out of the mill-annealed (as received)
16-mm thick plate stock. One of the flat faces of the
specimen was polished down to 1000 grit finish. After
thorough washing in soap, running water and 10 min
ultrasonication in acetone, these specimens were shot-
peened. The experimental variables of shot peening were
(1) peening medium (glass shots of 70–140 mesh (0.1–0.2
mm diameter) and stainless steel shots of 50–140 mesh) and
(2) blasting pressure (207, 345, and 414 kPa). Shot peening
was carried out at different blasting pressures for different
peening media for 450 s to form nanocrystalline surface.
Similar procedure is reported for producing nanocrystalline
surface on 304 SS [5]. The shots were not recycled to ensure
that only spherical shots peened the surface, and other
parameters were optimized to minimize the material
removal rate. After shot peening, the specimens were
annealed at 300 8C for 2 h, 350 8C for 1 h, and 500 8C
for 0.1 h. Insulated copper wire was soldered to the back of
the specimen for electrical connection, using silver-contain-
ing solder and acid flux. The maximum temperature
recorded on the specimens during soldering was of 69 8C,
which ensured no additional heat treatment cycles of the
specimens. Soldered specimens were mounted in epoxy
resin, exposing 1 cm2 of surface area, and the shot-peened
surface was polished with 1 ı̀m alumina slurry in order to get
as smooth a surface as possible. The epoxy-mounted
specimens were washed thoroughly with soap water and
lots of distilled water and sonicated in isopropyl alcohol for
10 min before introducing into the standard five-neck cell
for electrochemical polarization studies. Cyclic polarization
studies were carried out on the specimens in 2 M HCl+0.01
M NaF solution at 60 8C. Potential was varied at a rate of
0.5 mV/s from the open circuit corrosion potential to a more
noble potential corresponding to a current density of 5 mA/
cm2, and the potential was reversed back to the corrosion
potential. If pits are nucleated, a hysteresis in the polar-
ization curve could be observed during reverse scan of the
potential. A complete reversibility of the transpassive
current during the reverse potential scan indicates absence
of any localized corrosion. Potentiostatic passivation studies
were carried out in 0.5 M H2SO4 solution at 24 8C by
applying a constant potential of +400 mV and by recording
the passivation current. Mott–Schottky (M–S) measure-
ments to investigate the electronic properties of the passive
film were conducted at the conclusion of 1 h of passive film
571
growth at 400 mV. The measurements were initiated first at
the final passivation potential (+400 mV) and then as a
function of decreasing 100-mV potential steps in the active
direction down to
500 mV, using the CMS 300 electro-
chemical impedance system (Gamry Instruments). An AC
voltage signal of 10-mV amplitude at 3 kHz was super
imposed for 2 s at each potential step, and the resultant
impedance was measured and recorded as a function of
potential. This series of 2-s, 100-mV steps required a total
measurement time of b20 s, which is reported to be
insufficient to alter the passive-film structure [7]. The
interfacial capacitance C was calculated by the system
software using the relation C=(
ZU2pf)
1, where ZU is the
imaginary part of the impedance and f is the frequency.
Capacitance C is related, in turn, to the charge carrier
density, N D, by the following relation [7]
 
1 2 kT
¼ E
EFB
ð1Þ
C2 eee0 ND e
where, e=elementary electron charge, e 0=permittivity in
vacuum, e=dielectric constant, assumed 20.0 for Alloy 22 [8],
N D=charge carrier density, E=applied potential, E FB=flat
band potential, k=Boltzman constant, and T=temperature, K.
According to Eq. (1), the slope of the 1/C 2 vs. potential
plot gives the charge carrier density, N D, from the relation
2
ND ¼ ð2Þ
eee0 m
where m is the slope of the Mott–Schottky plot in the region
of interest. A positive slope indicates n-type semiconduc-
tivity and a negative slope p-type. The intercept at 1/C 2=0
on the potential axis gives E FB. All the potentials are
measured with reference to a Ag/AgCl electrode in
saturated KCl solution. The electrolytes were deaerated by
purging nitrogen continuously during experiments.
3. Results and discussion
Fig. 1 shows some typical results of cyclic polarization
experiments carried out in 2 M HCl+0.01 M NaF solution
at 60 8C on the specimens shot-peened at 345 kPa for 450
s with various low-temperature annealing treatments.
Tables 1 and 2 summarize the polarization results of other
specimens. In as shot-peened condition, the critical current
density for passivation (denoted as I cr in the Fig. 1)
increased, as compared to that of mill-annealed condition
for all the shot-peening conditions. However, the passiva-
tion current density (denoted as I p in the Fig. 1) decreased
with surface modification by shot peening. The critical
current density for passivation was observed to be a
function of shot-peening pressure, as the current density
increased with the increase in gas pressure, in general.
Low-temperature annealing of the shot-peened surface
resulted in reduction of both the passive current densities
572 K.S. Raja et al. / Materials Letters 59 (2005) 570–574

Table 2
Summary of anodic polarization results of nanocrystalline surface of Alloy
22 in 2 M HCl+0.01 M NaF solution at 60 8C
Surface condition Critical current Passive current
of Alloy 22 density for passivation, density
10
4A/cm2 10
5A/cm2
Mill-annealed 2.45 4.26
345 kPa–G–As-shot-peened 4.02 3.07
345 kPa–G–350 8C–1 h 1.52 2.04
414 kPa–G–As-blasted 5.43 3.6
414 kPa–G–300 8C–2 h 4.1 6.95
414 kPa–G–350 8C–1 h 2.34 2.87
414 kPa–G–500 8C–0.1 h 2.81 3.6
414 kPa–SS–As-blasted 5.18 3.43
414 kPa–SS–350 8C–1 h 3.51 3.39
The specimens were shot-peened at 345 kPa for 450 s, using glass shots
(G), and at 414 kPa, using glass shots (G) and stainless shots (SS).
Fig. 1. Cyclic polarization of nanocrystalline surface of Alloy 22 specimens
in 2 M HCL+0.01 M NaF solution at 60 8C. The specimens were shot-
peened at 345 kPa for 450 s, using glass shots. One specimen was tested in
as-shot-peened condition. The other one was shot-peened and annealed at annealing temperatures, especially 350 8C. Further, peen-
350 8C for 1 h. Polarization of the mill-annealed (MA) specimen is also ing medium (glass vs. stainless steel) also influenced the
included for comparison.
results. Transpassive potential also marginally increased
with shot-peening+annealing treatments, indicating more
stable passive films after surface nanocrystallization.
and critical current densities for passivation as compared to During passivation at 400 mV (Ag/AgCl) in 0.5 M
the shot-peened specimens without heat treatment. How- H2SO4 solution at 24 8C, the passive current decayed
ever, there were some exceptions to the above observation. obeying the relation
For example, specimens shot-peened at 207 kPa+annealed
at 500 8C for 0.1 h, and shot-peened at 414 kPa+annealed i ¼ i0 ðt=t0 Þ
n ð3Þ
at 300 8C for 2 h showed higher critical and passive
current densities as compared to mill-annealed and as-shot- where i=passive current density, i 0=oxidation current of
peened specimens. In general, a decrease in passive current bare metal, t 0=time at which current starts to decay,
density could be observed after shot-peening treatment, t=time,
n=exponent of current decay. Higher i 0 values
which further decreased with low-temperature treatment. It were observed on the as-peened specimens and the mill-
could be observed that lower shot-peening pressure annealed specimens. With low-temperature annealing, the
required lower annealing temperature to impart better passive current density decreased substantially following
electrochemical properties. For example, specimens shot- the trend of cyclic polarization results. Fig. 2 illustrates
peened at 207 kPa showed improved corrosion resistance the Mott–Schottky measurement carried out after passi-
when annealed at 300 8C. Annealing at 350 and 500 8C vating the shot-peened (207 kPa)+annealed specimens at
progressively increased the corrosion currents. Whereas, at
higher peening pressures (345 and 414 kPa), increased
corrosion resistance was observed at relatively higher

Table 1
Summary of anodic polarization results of nanocrystalline surface of Alloy
22 in 2 M HCl+0.01 M NaF solution at 60 8C
Surface condition Critical current Passive current
of Alloy 22 density for passivation, density
10
4A/cm2 10
5A/cm2
Mill-annealed 2.45 4.26
207 kPa–G–As-shot-peened 4.65 3.12
207 kPa–G–300 8C–2 h 2.37 2.9
207 kPa–G–350 8C–1 h 2.93 4.25
207 kPa–G–500 8C–0.1 h 3.18 8.45
207 kPa–SS–As-shot-peened 3.61 1.9 Fig. 2. Mott–Schottky measurements on nanocrystalline surface of Alloy 22
207 kPa–SS–350 8C–1 h 2.54 1.9 after passivation at 400 mV in 0.5 M H2S04 at 24 8C. The specimens were
The specimens were shot-peened at 207 kPa for 450 s, using glass shots (G) shot-peened at 207 kPa for 450 s and annealed at different temperatures for
and stainless shots (SS). different times.
 K.S. Raja et al. / Materials Letters 59 (2005) 570–574 573

400 mV for 1 h in 0.5 M H2SO4 solution at 24 8C. critical current density of the as-peened specimens during
Positive slope of the plots indicate an n-type semi- cyclic polarization (Tables 1 and 2) could be attributed to the
conductor film. The slope of the Mott–Schottky plot increase in the density of localized states due to structural
became shallower with shot peening, indicating increase inhomogeneities. During the low-temperature annealing, the
in charge carrier density, as described in the Eq. (2). dislocation density and other structural defects decreased,
Table 3 summarizes the results of Mott–Schottky measure- which resulted in a decrease in critical current density for
ment. The shot-peened specimens showed increased charge passivation. As the charge carriers can be considered point
density as compared to the mill-annealed specimen. The defects [10], decrease in charge carrier density upon
charge density was observed to decrease with low-temper- annealing (Table 3) could be correlated to the decrease in
ature annealing. Flat band potential became nobler as the structural defects of nanocrystalline surface. Low temper-
charge density increased. ature annealing treatments have been observed to result in
Li et al. [5] evaluated the mechanical properties of the well defined nanosize grain boundaries and improved
nanocrystalline surface of 304 SS and correlated the interfacial bonding between the nanocrystalline surface and
improved corrosion resistance with the enhanced mechan- the parent substrate, as compared to those of as-peened
ical properties. Shot peening or shot blasting of metallic condition [5,6]. Although the critical current density for
surfaces caused severe plastic deformation and formation of passivation of most of the shot-peened specimens (even after
high density of dislocations, leading to nanoscale cell annealing) was higher than that of mill annealed specimen,
structures. Liu et al. [3] observed a 30-Am thick nano- the passive current density was lower. Higher current and
crystallized surface layer after ultrasonic shot-peening therefore increased dissolution of alloying elements (before
treatment, with the grain size varied from 10–100 nm on reaching the passivation potential) could have resulted in
316 L stainless steel surface. Wang and Li [5] also reported generation of vacancies or divacancies, which subsequently
a 20-nm grain size of the sandblasted 304 SS surface. These diffused into the subsurface [11]. Cross diffusion of metal
authors reported no significant change in grain size after vacancies and higher dislocation densities at the nanocrystal-
low-temperature annealing of the sandblasted surface. Based line-surface layer could act as short circuit diffusion paths for
on the literature results, it is more likely that shot peening of passivation-promoting alloying elements to reach the surface
Alloy 22 surface for extended period of time (450 s) could and form a coherent passive film at the passive range of
have resulted in surface nanocrystallization. Improved potentials [5].
electrochemical properties of the shot-peened+annealed Surface modification of Alloy 22 by shot-peening+an-
specimens also support possible surface nanocrystallization. nealing treatments did not alter the type of semiconduc-
However, electron microscopy studies are required to be tivity of the passive film. Predominantly n-type behavior
carried out to substantiate this claim. could be observed from the Mott–Schottky plots. Gen-
During shot peening, as the surface was severely plastic- erally, flat band potential is considered as a theoretical
deformed, the passive film formed on the surface also could pitting protection potential in case of stainless steels, as
be considered as highly disordered because of nanoscale electrostatic potential gradient across the passive film is
dislocation structures. These defect structures introduce a absent at flat band potential [9]. Mott–Schottky measure-
high number of localized electron levels close to the band ments were not carried out in pitting environments in this
edges and alter the forbidden energy gap [9]. The higher study. Therefore, flat potentials of different nanocrystal-
line surface specimens do not represent their pitting
protection potential. Flat band potential varies with pH of
Table 3 the solution and the redox couple present in the environ-
Summary of Mott–Schottky analyses of nanocrystalline surface of Alloy 22 ment [12]. In this study, more positive values of flat band
after 1 h passivation at 400 mV in 0.5 M H2SO4 at 24 8C potential indicate better stability of the passive film
Surface condition Flatband Charge (donor) density during anodic polarization, as the passive film of Alloy
of Alloy 22 potential of passive film 22 is of n-type semiconductor [13]. The difference
mV(Ag/AgCl) (1 /cm3)
between the transpassivation potential (E tp) and the flat
Mill-annealed
205 2.981021
band potential (E FB), E tp
E FB, was observed to be a
207 kPa–G–As-peened
153 6.131021
207 kPa–G–300 8C–2 h
167 5.881021 function of the difference between the energy of the
207 kPa–G–350 8C–1 h
160 5.331021 Fermi level and valence band edge of the passive film
207 kPa–G–500 8C–0.1 h
115 7.411021 [13]. Analyses of the Mott–Schottky plots indicated that
207 kPa–SS–As-peened
188 3.351021 the as-peened specimens showed larger capacitance values
207 kPa–SS–350 8C–1 h
163 3.921021
(lower 1/C 2 values) at the passivation potential than the
345 kPa–G–As-peened
120 6.911021
345 kPa–G–350 8C–1 h
195 3.081021 most of other specimens. Assuming that the width of
414 kPa–G–As-peened
155 6.101022 space charge layer associated with the capacitance type
414 kPa–G–300 8C–2 h
161 3.861021 behavior is equal to the passive film thickness, the
414 kPa–G–350 8C–1 h
120 4.901021 capacitance, C, and the passive film thickness can be
414 kPa–G–500 8C–0.1 h
165 4.501021
related as C=e 0eA/d, where A=area of the specimen and
574 K.S. Raja et al. / Materials Letters 59 (2005) 570–574
d= thickness of the passive film. In as-peened condition,
the passive film was observed to be thinner than mill-
annealed condition. The low-temperature annealing treat-
ment showed relatively thicker passive films than that of
as-peened specimens.
4. Conclusions
Surface modification of Alloy 22, a nickel base Ni–
22Cr–13Mo–4W–3Fe alloy, by shot-peening+low-temper-
ature annealing process was found to improve the corrosion
resistance in hot acid chloride environment.
The surface modification treatment did not alter the type
of semiconductivity of the passive film of Alloy 22. Higher
charge carrier density and nobler flat band potential were
observed in the as-peened condition.
Low-temperature annealing after shot peening resulted
in lower critical current density for passivation and lower
passive current density. The potential range at which
passivation was maintained increased with surface
treatments.
Acknowledgement
This work was supported by the US Department of
Energy through Contract No. DE-FG02-04ER63819.
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