J. CHENG et al.: EFFECT OF PARTICLE IMPINGEMENT ON ELECTROCHEMICAL PROPERTIES ...
275–281
EFFECT OF PARTICLE IMPINGEMENT ON ELECTROCHEMICAL
PROPERTIES OF STAINLESS STEEL IN A JET FLOW
VPLIV TRKOV DELCEV V REAKTIVNEM TOKU NA
ELEKTROKEMIJSKE LASTNOSTI NERJAVNEGA JEKLA
Jiarui Cheng
1
, Ningsheng Zhang
1,2
, Yihua Dou
3
, Zhen Li
3
, Yinping Cao
3
1
Xi’an Jiaotong University, State Key Laboratory of Multiphase Flow in Power Engineering, 28 Xianning West Road, Xi’an City, Shaanxi
Province 710049, China
2
Xi’an Shiyou, University, Department of Petroleum Engineering, 18, Dianzi 2
nd
Road, Xi’an City, Shaanxi Province 710065, China
3
Xi’an Shiyou University, Department of Mechanical Engineering, Xi’an City, Shaanxi Province 710065, China
cjr88112@163.com
Prejem rokopisa – received: 2017-06-21; sprejem za objavo – accepted for publication: 2017-12-21
doi:10.17222/mit.2017.079
The objective of this research was to discuss the effects of physical impingement on the corrosion resistance of super 13Cr
stainless steel in a solid-liquid jet flow. Data from standard laboratory tests including open-circuit potential (OCP), polarization
potential, current and surface morphology was obtained. In addition, the passivation process at a changing flow velocity and
after particle impacts were discussed using a point-defect model (PDM). The experimental results showed that particle impacts
affect not only the electrochemical parameters but also the apparent structure of a sample, thus weakening the surface corrosion
resistance of stainless steel. An uninterrupted particle impact damages loose passive films, decreases the electric potential and
increases the current density. When the change in the potential reaches a stable state, the metal potential is gradually increased
due to the influence of passivation; the passivation rate is the most significant at the beginning of the passivation and at a low
flow velocity.
Keywords: solid-liquid two-phase flow, electrochemical property, passive film, repassivation
Predmet raziskave je bil raziskati vplive fizikalnih trkov na odpornost proti koroziji super nerjavnega jekla 13 Cr v toku me{a-
nice kapljevine in trdne faze. Avtorji so podatke zbrali s pomo~jo standardnih laboratorijskih testov, kot so: potencial v odprtem
tokokrogu (OCP; angl.: open-circuit potential), povr{inska morfologija, polarizacijski potencial in tok. Dodatno so uporabili
model to~kovnih napak (PDM; angl.: Point Defect Model) za razlago procesa pasivacije v spreminjajo~ih se pogojih hitrosti
pretoka medija po trkanju delcev na povr{ino vzorca. Rezultati preizkusov so pokazali, da trki delcev ne vplivajo samo na
elektrokemi~ne procese temve~ tudi na navidezno strukturo vzorca in s tem se slabi protikorozijska odpornost nerjavnega jekla.
Neprekinjeno mesebojno trkanje (udarjanje oz. zadevanje) delcev po{koduje pasivni film in tako zmanj{a elektri~ni potencial ter
pove~a gostoto toka. Ko sprememba potenciala dose`e neko stabilno vrednost, potencial kovine postopno naraste zaradi vpliva
pasivacije in hitrost pasivacije je najbolj pomemben faktor na za~etku pasivacije pri majhni hitrosti pretoka.
Klju~ne besede: dvofazni tok kapljevina-trdno, elektrokemijske lastnosti, pasivni film, repasivacija
1 INTRODUCTION
Stainless steel usually has the ability to resist flow-
media corrosion due to its passive behavior. However, if
the passive films are ruptured by the fluid shear stress or
solid-particle impacts, fresh metal will be exposed to
corrosive media, which may lead to potential and
current-density variations. This phenomenon is usually
called erosion-enhanced corrosion.
1
The dissolution and passivation of passive films
coexist in the electrochemical reaction system of the
metal surface. Once the passive films are ruptured, which
is called "the additive",
2
the dissolution reaction will take
place as the dominate process. In this case, the passi-
vated atoms on the metal surface continuously oxidize
and form an oxide film to resist the corrosion reaction.
This process includes the oxygen mass transfer from the
main flow region to the metal surface,
3
migrations of
electrons in the films
4
and the oxidization of the
Fe-alloy.
5
Some researchers defined the repassivation
kinetics, which was determined with the anodic-current
density, to indicate the growth of passive films.
6
The
repassivation kinetics was measured with several
experimental methods such as the particle-impact test,
7,8
fracture test,
9
slower electrode straining
10
and scratching
test.
11
The common difficulties in these measurement
processes were the control of the film rupture and the
monitoring of the repassivation. This specifically
involves obtaining the impact velocity, angle and oxygen
concentration near the surface under the flow condition.
In addition, particle impacts may cause the open-circuit
potential of stainless steel to increase with time until it
attains the pitting potential.
12
In this work, the dissolution and passivation of stain-
less-steel surface are controlled with a quantitative part-
icle injection. The current density and the open-circuit
potential are monitored before and after the injection of
particles at different flow velocities. Moreover, the pola-
rization potential, polarization current density and sur-
face morphology are also obtained to investigate the
effect of particle impact on the stainless-steel corrosion
Materiali in tehnologije / Materials and technology 52 (2018) 3, 275–281 275
UDK 620.1:67.017:691.714.018.8 ISSN 1580-2949
Original scientific article/Izvirni znanstveni ~lanek MTAEC9, 52(3)275(2018)

resistance. Finally, the effect of particle impact on the
passivation rate is discussed in detail.
2 EXPERIMENTAL PART
Electrochemical-corrosion-resistance tests were per-
formed using a solid-liquid two-phase jet-flow system.
Unlike in the previous research,
7,8,11,12
experimental
particles were collected with a rectangle box after the
particles impacted the sample surface. This could ensure
that most particles impacted the specimen only once in
each particle injection and that we could control the spe-
cific particle impact time.
2.1 Jet-flow system
The jet-flow system consisted of a stainless-steel
tank, a centrifugal pump, a temperature sensor and a
pressure sensor, a magnetic flowmeter (8712HR, Rose-
mount. Co., America) and a jet test section (Figure 1).
Electrochemical measurements were operated using the
jet tester as shown in Figure 2. An experimental nozzle
(length: 200 mm, inner diameter: 10 mm) was used at an
impact angle of 90° (normal incidence) and the jet-flow
velocity was changed from 3 m/s to 9 m/s. A three-elec-
trode system was incorporated into a slurry erosion rig
for the open-circuit potential and potentiostatic testing.
The saturated calomel reference electrode (SCE), placed
in the test chamber, was connected to the standard three-
electrode system. A long platinum wire was used as the
counter electrode (CE). During the monitoring, the
polarization curves were recorded by changing the elec-
trode potential at a sweep rate of 0.2 mV/s. The sample
surfaces were examined with scanning electron micro-
scopy (SEM) and an energy dispersive spectrometer
(EDS) (JSM-6390). (JSM-6390, JEOL. Co., Japan).
2.2 Experimental set-up
The chemical composition of the super 13Cr stainless
steel, used in this experiment, is given in Table 1, and
the sample with dimensions of 20 mm × 20 mm and a
thickness of 5 mm is shown in Figure 2. Firstly, each
specimen surface was encased in a polymethyl metha-
crylate (PMMA) insulating sheet, except the test surface.
Secondly, the exposed surface was sealed with epoxy
resin and ground using SiC emery paper of grade 1200.
The test particles were made of bauxite, and their geo-
metric properties are shown in Table 2. A slurry elec-
trolyte solution of 3.5 % of mass fraction of sodium
chloride (NaCl) in double distilled water was used as the
circulation media. At the beginning of the experiment,
the pump was started and the frequency converter was
controlled until the flow-rate fluctuation was less than
0.01 m
3
/h. After that, the electrochemical workstation
(PARSTAT-2273, Princeton. Co., America) was used to
monitor the current and potential. A group of particles
(about 75±0.05 g, amounting to the number of
187500±125) was injected into the tank when the
electrochemical system was stable.
Table 1: Chemical composition of the super 13Cr stainless steel used
in the experiment
Composi-
tion (w/%)
CC rM oN iS iM nSP
Super 13Cr 0.022 13.22 0.94 4.81 0.26 0.45 0.0006 0.017
Table 2: Parameters of the particles used in erosion testing
Parameter
Diameter
(mm)
Mass
(mg)
Quantity
(n)
Value 0.6±0.03 0.4±0.05 187500±125
3 RESULTS
The growth and rupture of passive films occurred
simultaneously on the metal surface, and there was a
J. CHENG et al.: EFFECT OF PARTICLE IMPINGEMENT ON ELECTROCHEMICAL PROPERTIES ...
276 Materiali in tehnologije / Materials and technology 52 (2018) 3, 275–281
Figure 2: Jet test chamber, electrode arrangement and particle
morphology used in the experiments
Figure 1: Jet-flow system used in electrochemical experiments
Figure 3: Records of the corrosion current density in response to the
changes in the flow velocity at 0V vs. SCE

balanced relation between them in the flow condition.
According to the results of Z. B. Zheng’s research,
13
there is a large difference between depassivation and
repassivation in a sand-containing NaCl solution when
the flow velocity is below or greater than the critical
velocity. In this work, the responding current densities of
super 13Cr stainless steel are presented in Figure 3. The
critical velocity that separates the regions of non-observ-
able and significant responses was 7 m/s. Therefore, the
open-circuit-potential monitoring and the polarization
measurement were characterized at velocities of (3, 6
and 9) m/s in order to study the depassivation and
repassivation of stainless steel in different electroche-
mical response ranges.
3.1 Monitoring of the open-circuit potential and cur-
rent density
Figure 4 shows that the OCP changes with the test
time at different flow velocities during two particle
injections. There are three obvious regimes, including
the passive-film formation (Regime I), the breakdown
(Regime II) and the recovery (Regime III) during an
injection process.
In Regime I (Figure 5), each potential spike shows a
rapid fall, followed by a relatively slow exponential rise
back to the base line due to the pits persistently growing
and metal passivation. The potential increases slowly
after a few minutes and shows a small fluctuation. At
this moment, metastable pits can initiate and propagate if
the potential is below the pitting potential. For example,
the OCP changes in a tight range between -0.20 V and
-0.02 V (SCE) at the velocity of 9 m/s, and then it gra-
dually steadies at -0.17 V (SCE).
In Regime II (Figure 6), the value of the OCP
changes in the negative direction when particles are
injected into the jet-flow system. Part of the passive
films ruptures immediately and forms slowly after the
particle impact in a few seconds. It causes the potential
to change negatively from -0.165 V to -0.57 V
(v = 9 m/s) and the current density to increase from
28 μA to 57 μA. In this process, the decrease in the OCP
and the increase in the current density are changed
nonlinearly because of the nonlinear growth of fresh
areas. Moreover, when the particles stop to impact the
metal surface, the flow system and electrochemical
system need a certain period of time to become stable.
The OCP increases slowly, with a slight concussion, to
-0.29 V (SCE) in a single-phase flow, containing 3.5 %
mass fractions of NaCl. The difference between the
potential values before and after the particle impacts is
equal to 0.12 V (SCE).
After that, the particles are injected into the system
again with the aim to confirm that the behavior of the
breakdown and recovery of a passive film is repeatable.
The minimum values of the OCP in the process of the
first and second particle injection are very close. There-
fore, when the potential goes below a certain value, the
potential will no longer decrease obviously. In addition,
after the metal-surface passivation, the stable potential is
generally lower than the initial potential before the
injection of particles. Thus, the corrosion resistance of
the repassivated film is not as strong as before because
electrode potential deviates negatively from equilibrium
potential.
3.2 Polarization measurement
A polarization-curve test was used to compare the
current densities and potentials before and after the
J. CHENG et al.: EFFECT OF PARTICLE IMPINGEMENT ON ELECTROCHEMICAL PROPERTIES ...
Materiali in tehnologije / Materials and technology 52 (2018) 3, 275–281 277
Figure 6: Records of open-circuit potential and current density in res-
ponse to particle impingement at the velocity of 9 m/s: a) single-phase
solution, b) solid-liquid two-phase solution
Figure 4: Open-circuit potentials under the solid-liquid jet flow at the
velocities of (3, 6 and 9) m/s, respectively
Figure 5: Open-circuit potentials of super 13Cr stainless steel under
the jet flow free of particles

particles impacted the sample. Figure 7a shows the
polarization curves for super 13Cr stainless steel at
different flow velocities in a single-phase solution. When
the flow velocity is increased from 3 m/s to 9 m/s, the
anodic polarization curves move towards the negative
direction, and there is no obvious passivation region of
each anode polarization curve. The corrosion potential
E
corr
at the flow velocity of 9 m/s is slightly lower than at
3 m/s and 6 m/s. And the anodic dissolution current at a
higher anodic potential at the flow velocity of 3 m/s is
even lower than that at 6 m/s. In addition, the metastable
pitting activity can be seen at the velocity of 3 m/s as
revealed by a series of transients from 0.68 V to 0.85 V.
The polarization curves at different flow velocities
under particle impingement are presented in Figure 7b.
Like the polarization curves in the single-phase solution,
they show no obvious passivation region of each anode
polarization curve. However, anodic polarization causes
violent fluctuations at the velocities of 6 and 9 m/s. The
anodic current densities change in the range of 7.3–64.7
mA for the jet velocity of 6 m/s and 6.9–48.4 mA for the
jet velocity of 9 m/s. The passivation current density
varies continuously and tends toward a relatively stable
value of i
p
. Meanwhile, this current density i
p
at the
velocity of 6 m/s is close to that at 9 m/s, which indicates
that the fluctuation of i
p
is more affected by particle
impingement than the flow velocity.
3.3 Surface morphology
A typical particle impact crater on a sample surface is
shown in Figure 8. The outer-circumference area suffers
from an occasional impact of a few particles, and it has
no uniform thinning of the surface. The center area of the
sample is subjected to repeated particle impacts and has
craters, platelets and extruding lips on the surface, as
shown in Figure 9a. For the sake of contrast, the surface
of the same sample after1hofe xposure to the single-
phase flow containing 3.5 % of mass fractions of NaCl at
9 m/s is revealed in Figure 9b. Numerous, a few μm
wide, lips or platelets are not obvious; they are the result
of mechanical cutting or corrosion. The convex parts
around the craters are worn by the fluid shear stress and,
consequently, more chloride ions make incursions into
material’s body. In fact, a pit of around 17.5 μm (Figure
10) in width is found on the sample immersed in the
J. CHENG et al.: EFFECT OF PARTICLE IMPINGEMENT ON ELECTROCHEMICAL PROPERTIES ...
278 Materiali in tehnologije / Materials and technology 52 (2018) 3, 275–281
Figure 9: SEM micrographs of the erosion surface of super 13Cr
stainless steel at the jet velocity of 9 m/s: a) surface topography after
particle impact, b) erosion surface morphology after corrosion
Figure 7: Polarization curves for super 13Cr stainless steel in the
flowing condition
Figure 8: Erosion surface morphology on the outer circumference
surface

NaCl solution, which is larger than the ones reported in
M. Fin{gar and I. Milo{ev’s research
14
(pits of around 2.5
μm in width). It is confirmed that the anti-pitting ability
is weakened by particle impingement, which makes the
metal surface not smooth in the flow condition. To assess
the chemical composition of the erosion surface before
and after corrosion, EDS was performed on the same
area of the center surface (Figure 11). The oxygen peak
is presented as oxidation while iron and chromium are
present in both the metallic and oxide states, and
chlorine slightly increases after the passivation for 1 h.
Hence, there is a loose surface of the metal, caused by
the impact of particles, which is more susceptible to
chloride ion corrosion.
4 DISCUSSION
As shown in Figure 4, the surface potential impacted
by the particles will not be reduced indefinitely, but there
is a minimum value. In this work, the number of
particles that flow out of the nozzle every second is more
than 5000, which leads to the passive time of the unit
erosion area being less than 0.05 s. Most of the passive
films, therefore, are ruptured by the persistent impact of
particles until the exposed areas tend not to change. We
use the change in the potential in such a way that it
reflects the passivation characteristics of the surface
during particle impacting and after particle impacting.
According to the point defect model, the voltage drop
across the film/solution interface is defined with
Equation (1):
15
ΔEE E p H =++
01
 (1)
where E
0
is the zero voltage drop,  is the polarizability
of the film/solution interface, and is the dependence of
the voltage. If the effect of pH on the voltage drop is not
taken into account, a passive fitting equation is obtained
in Equation (2):
EEE
t
=+ −
⎛ ⎝ ⎜ ⎞ ⎠ ⎟ 01
exp
 (2)
where  is the decay constant, E
0
is the minimum value
of the OCP during the particle impact on the metal sur-
face, and t is the passive time after the particle impinge-
ment. According to the experimental data shown in
Figure 4, the passivation rate can be indicated by the
slope of a OCP curve, called passivation coefficient  in
Equation (3):
 
=≈= −
⎛ ⎝ ⎜ ⎞ ⎠ ⎟ Δ
Δ
E
t
dE
dt
E
t 1
1
exp (3)
J. CHENG et al.: EFFECT OF PARTICLE IMPINGEMENT ON ELECTROCHEMICAL PROPERTIES ...
Materiali in tehnologije / Materials and technology 52 (2018) 3, 275–281 279
Figure 12: Continuous changes in the potential at different flow velo-
cities
Figure 11: EDS analysis of the chemical composition of the stain-
less-steel surface after: a) particle impact and b) corrosion
Figure 10: SEM view of defects formed on the erosion surface
immersed for1hina3.5%ofmass fraction of NaCl solution

If the collection of particles is cancelled, the particles
will impact the sample surface without interruption. At
this moment, we get the curves of the potential changes
under different flow velocities in the solid-liquid solution
(Figure 12). Here, E
1
and E
2
,  1
and  2
represent the
potential at the beginning and the end of the passivation
at the same flow velocity, the potential reduction during
the changing flow velocity and the increase in the
potential during the passivation process. Table 3 shows
detail values of each parameter. It is found that not only
the potential (E
1
and E
2
) but also the change in the po-
tential ( 1
and  2
) decrease with the increasing velocity.
The decrease in E
2
indicates that the metal surface is
more susceptible to corrosion, and the decrease in E
2
reflects that the passivation ability of the stainless-steel
surface decreases at high flow velocities. Thus, the rule,
according to which the coefficient decreases with the
increasing two-phase flow velocity, is obtained. How-
ever, the effect of the increasing velocity on the reduc-
tion of the potential is not always significant, as it may
weaken when the flow velocity increases, which can be
seen from the change in  1
. The difference in the
potential for the flow velocities of 7 m/s and 8 m/s is
close to 0.04 V, which is much smaller than the potential
absolute value.
Table 3: Values of passivation parameters in potential monitoring (the
test time for each flow velocity is 1200 s)
Jet-flow
velocity
(m/s)
Potential
Potential
difference
Passivation coefficient
E 1/V E
2/V  1/V  2/V  3 - -0.12 - - -
4 -0.23 -0.15 0.11 0.08 1.33
5 -0.27 -0.17 0.12 0.10 1.67
6 -0.28 -0.24 0.11 0.04 0.67
7 -0.31 -0.28 0.07 0.03 0.50
8 -0.32 -0.28 0.04 0.04 0.67
If the particles are collected after impacting the
sample, the passivation coefficient can be obtained by
fitting the potential curves for the single-phase flow.
According to the passivation curves (Figure 4), the
decay constant  changes in the negative direction with
the increasing jet-flow velocity, as shown in Table 4.
The smaller decay constant  refers to the passivation
coefficient  decreasing over the time, which means that
the passivation reaction is more difficult to obtain at high
flow velocities. As shown in Figure 13, the passivation
coefficient has the maximum value at the beginning of
passivation, which decreases remarkably as time goes
on. When  is less than 0.01, the increase in the OCP is
also less than 0.01 V in every second. At this time, the
passive reaction and the active reaction can be
considered to be balanced. However, the final OCP after
the passivation is lower than the initial result before the
particle impact, which may be caused by a high vertical
particle impact.
Table 4: Parameters of two fitting curves at different flow velocities
Velocity
(m/s)
First passivation Second passivation
E 1 (V)  E
1 (V)  3 3.9 2.3 4.7 3.5
6 2.7 1.8 3.3 1.8
9 1.9 0.8 1.2 0.9
5 CONCLUSIONS
A solid-liquid-jet-flow experiment was carried out to
evaluate the effect of particle impingement on the
electrochemical characterization of super 13Cr stainless
steel at different flow velocities. At the macroscopic
level, the open-circuit potential changes non-linearly in
the negative direction and the current density changes in
the positive direction in the solid-liquid two-phase flow.
The OCP at the end of the passivation is lower than
before the particle impacts. This indicates that particle
impacts can weaken the corrosion resistance of stainless
steel in the chloride medium. However, there is a limit to
this weakening effect. For example, in the process of
multiple impacts at the same velocity, the minimum
potentials are the same at each particle impact. Mean-
while, the decrease in the potential gradually stabilizes
with the increasing flow velocity. Beyond this, the higher
the impact velocity of particles, the lower is the passiva-
tion coefficient per unit of time. At the same time, the
passivation coefficient reaches the maximum value and
then drops with the increasing time. In addition, at the
microscopic level, the impact of each small particle has
an impact on the metal-surface properties.
This effect mainly reflects the following aspects:
First, anodic polarization is constantly disturbed by part-
icle impacts between the activated state and the passive
state. Second, pitting corrosion is caused by tiny ions
that more easily penetrate into the loose oxide layer.
J. CHENG et al.: EFFECT OF PARTICLE IMPINGEMENT ON ELECTROCHEMICAL PROPERTIES ...
280 Materiali in tehnologije / Materials and technology 52 (2018) 3, 275–281
Figure 13: Passivation-rate coefficient versus jet-flow velocity over
time

Acknowledgement
This work was supported by the National Natural
Science Foundation of China (grant no. 51674199), and
it was also performed by The Research Institute of
Safety Evaluation and Control of Completion Test
System.
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