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Impedance Monitoring of Carbon Steel Cavitation

Erosion under the Influence of Corrosive Factors

Article in Journal of The Electrochemical Society · January 2008

DOI: 10.1149/1.2840619

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P44 Journal of The Electrochemical Society, 155 共4兲 P44-P49 共2008兲
0013-4651/2008/155共4兲/P44/6/$23.00 © The Electrochemical Society

Impedance Monitoring of Carbon Steel Cavitation Erosion

under the Influence of Corrosive Factors
J. Rylz and K. Darowicki
Department of Electrochemistry, Corrosion and Materials Engineering, Gdansk University of Technology,
80-952 Gdańsk, Poland

The degradation of carbon mild steel under cavitation erosion–corrosion exposure was studied by means of a 20 kHz ultrasonic
device with a piezoelectric inducer. Possibilities of estimation of material failure by current measurement techniques are presented
and discussed. The effect of cavitation exposure of the mild steel has been investigated in situ with the dynamic electrochemical
impedance spectroscopy technique. Estimation of the surface degradation rate is enabled by an adequate equivalent circuit
selection. A dynamic impedance method was used to verify the impedance parameters online during the measurement. These
measurements are assisted by estimation of the weight loss function commonly used for the evaluation of erosion–corrosion
resistance of materials.
© 2008 The Electrochemical Society. 关DOI: 10.1149/1.2840619兴 All rights reserved.

Manuscript submitted October 1, 2007; revised manuscript received January 11, 2008. Available electronically March 3, 2008.

Cavitation erosion is a very common effect in a turbulent flow
environment, such as ship propellers, hydrofoils, turbines, pumps,
and heat exchangers. Erosion degradation of installation in direct
contact with imploding cavitation bubbles is in most cases very
undesirable, resulting in frequent breakdowns and shortening their
operation time.1 It is a complex phenomenon involving the interac-
tions of hydrodynamic, metallurgic, mechanical, and chemical fac-
tors and should be considered as a unique type of material damage
in its own right.2 Some research has been carried out to compare
cavitation erosion resistance with other mechanical properties: hard-
ness, strain energy, ultimate resilience, or fatigue resistance;2,3 how-
ever, no direct connections were assigned between the effect of cavi-
tation and other mechanical treatments.
Cavitation is mainly mechanical in its nature, although this type
of damage is more severe when cavitation erosion and electrochemi-
cal corrosion act synergistically. Wood et al.4,5 pointed out some
examples for synergistic interaction between corrosion and erosion:
removal of the corrosion product film from the surface, exposing
bare reactive metal; local acidification at erosion sites, accelerating
corrosion rates and prohibiting film formation; lowering the fatigue
strength of metal by corrosion; removal of work-hardened surfaces
by corrosion processes which expose the underlying base material to
erosion mechanisms, etc. The overall damage arising from erosion
and corrosion, including the interaction between them, is termed
cavitation erosion–corrosion. Many researchers focused on the de-
termination of this synergistic effect for different metals and alloys.
Kwok et al.6 observed that, for some investigated alloys, the
fractional weight loss due to pure corrosion during cavitation expo-
sure in 3.5% NaCl solution ranged up to 12%, while that due to the
synergistic effect between erosion and corrosion ranged as high as
66%. Wood and Fry7 concluded that the synergism occurring in the
presence of mild corrosion was responsible for 50% of the overall
mass loss rate.
It was pointed out by Vyas and Hannson8 that, for some metals,
the existence of passive films may accelerate or decelerate corro-
sion, depending on the intensity of the cavitation and the metallur-
gical state of the stainless steel specimens. A highly adhesive, resis-
tant, and quickly repassivating layer is important for the reduction of
corrosion induced by cavitation erosion.
Despite the influence of corrosion and the synergistic corrosion/
erosion factor on cavitation, there have been only a few electro-
chemical methods used to study the cavitation phenomenon up to
now: Kwok et al.6 investigated the free corrosion potential of a
sample under cyclic cavitation exposure; Engelberg and Yahalom9
constructed polarization curves of steel specimens eroded in an ul-
trasonic vibratory cavitation device.
z
E-mail: jacekr@chem.pg.gda.pl
The issue of constant monitoring of construction in order to pre-
vent them from cavitation erosion–corrosion failure, as well as the
determination of the proper time of replacement of eroded parts, is
crucial. This problem is especially important in the case of pumps,
turbines, or heat exchangers where direct, visual determination of
erosion–corrosion damage is very hard to obtain, if not impossible.
Currently, there is no unequivocal information in the literature on
this subject.
The aim of this research is the determination of the cavitation
influence on the change of the electrochemical parameters of the
system, and verification of the dynamic electrochemical impedance
spectroscopy 共DEIS兲 technique for the effective monitoring of cavi-
tation erosion–corrosion effects. DEIS can be used to evaluate the
kinetics of the cavitation degradation process as well as provide
quantitative and qualitative information on the corrosion factors in-
fluencing erosion–corrosion. Obtained results were compared with
the mean depth of penetration rate 共MDPR兲 function, which is a
standard method for the determination of cavitation erosion resis-
tance.
Experimental
Cavitation was induced in vibratory facilities, according to the
ASTM G32 Standard.10 The nature of the material damage was be-
lieved to be similar to that obtained in hydrodynamic facilities. Most
experiments in laboratory conditions are performed on vibratory ap-
paratus, because of low erosion rates achieved in hydrodynamic
cavitation tests. A vibratory facility gives the possibility of electro-
chemical measurement, together with the analysis of the influence of
chemical constitution, temperature, and pH. Vibratory apparatus is
standardized and the most commonly used technique for cavitation
generation in laboratory conditions. A schematic graph of the system
used for cavitation erosion degradation is presented in Fig. 1.
Measurements were carried out on mild steel. The chemical con-
stitution is listed in Table I. Prior to each experiment, the samples
were mechanically polished with 500–1600 gradation abrasive pa-
per. Samples were mounted 1 mm below the horn of the piezoelec-
tric transducer. The surface area exposed for cavitation erosion deg-
radation was 1.22 cm2.
Electrochemical investigations were carried out in a three-
electrode system, with the measured sample as the working elec-
trode, Ag/AgCl as the reference electrode, and platinum mesh as the
counter electrode. All potentials in this article refer to a Ag/AgCl
electrode. The solution prepared for the investigations was 3%
NaCl. Despite the electrodes, every part immersed in the solution
was an insulator to electric current. The cavitation excitation had a
cyclic character, with an on/off period of 30 and 90 s, respectively.
The measurement setup consisted of the electrochemical mea-
surement software Gamry International, an ELPAN EG20 linear
sweep generator, and a National Instruments PCI 6120 card that
generated the perturbation signal, registered the voltage perturba-

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 Journal of The Electrochemical Society, 155 共4兲 P44-P49 共2008兲 P45

Figure 1. Schematic diagram of a vibratory cavitation facility with electro-

chemical test system.

tion, and the current response signals. Impedance measurements

were executed for the frequency range 45 kHz to 7 Hz. A sampling
frequency of 125 kHz resulted from the measurement card settings
being at the authors’ disposal. The multisinusoidal signal composed
of 20 sinusoids was utilized. Depending on the applied frequency,
the amplitudes of the sinusoidal signals ranged from 5 to 20 mV.

Results and Discussion

Figure 2 represents changes of the current in the potentiostatic
mode due to the cavitation exposure. The effect of the cyclic
erosion–corrosion influence was measured with a forced potential,
Ep, equal to the corrosion potential measured in quiescence condi-
tions. Repeatable changes of current due to the cavitation erosion–
corrosion exposure were evident. The current flowing through the
system under the cavitation exposure was called icav. Values of the
icav shift have a cathodic direction, compensating the anodic shift of
corrosion potential. This effect may be connected with the increase
of the transport of oxygen in the liquid jet during the ultrasonic
stirring or with the generation of cavitation bubbles. In the research
of Luo et al.,11 bubbles filled with oxygen were delivered in the
neighborhood of the sample surface, resulting in a similar shift of
the corrosion potential of the measured sample.
The classic approach to estimate the cavitation erosion resistance
is Re, based on the converse of the mass loss function of measured
sample 共Eq. 1 and 2兲, most often called the MDPR2,6,12
MDPR = 冉 ⌬W
10A␳⌬tcav
冊 关1兴
Figure 3. Cavitation exposure effect as 共a兲 MDPR function and 共b兲 current
icav.
Re = 共MDPR兲−1 关2兴
where MDPR determines the mass loss rate ⌬W in time ⌬t, A stands
for the sample surface exposed to the cavitation impact 共1.22 cm2兲,
and ␳ is the sample density 共7.85 g/cm3兲. The MDPR vs time of
cavitation exposure, tcav, relationship can be seen in Fig. 3a.
Degradation due to cavitation exposure is a complex process.
The total mass loss 共T兲 determined as the MDPR function is a sum
of three components: mechanical erosion 共E兲, electrochemical cor-
rosion 共C兲, and the synergetic effect between erosion and corrosion
共S兲
TMDPR = EMDPR + CCP + S 关3兴
The corrosion component of the mass loss due to cavitation was
estimated from the polarization curve; the erosion rate due to cavi-
tation was estimated after cavitation exposure of samples in distilled
water, and the synergistic effect was calculated as a difference
T − 共E + C兲
The MDPR function value of the above components for tcav
= 60 min is listed in Table II. The total cavitation erosion–corrosion
failure is, in the case of mild steels, strongly related to the joint
interaction of mechanical and electrochemical processes for mild
steels. Mild steel mass loss due to the synergetic effect ranged from

Table I. Chemical constitution of carbon mild steel.

Fe C S P Si Mn Cr Ni Cu
Figure 2. Influence of cavitation exposure on the electric current values in
potentiostatic mode. Bal. 0.22 0.05 0.05 0.35 1.10 0.30 0.30 0.30

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P46 Journal of The Electrochemical Society, 155 共4兲 P44-P49 共2008兲
Table II. MDPR mass loss function for tcav = 60 min. Ep
= −670 mV.
T 共␮m h−1兲 E 共␮m h−1兲 C 共␮m h−1兲 S 共␮m h−1兲
0.22 0.06 0.02 0.14
50 to 80% depending on the alloy composition and measurement
conditions.6,7,11 Measurements carried out by the authors confirmed
these results.
During the cavitation erosion–corrosion degradation of the inves-
tigated sample, a slight change of icav was evident in time. Figure 3b
shows the effect of cavitation exposure on icav. Correlation of the
cavitation resistance variation 共as an MDPR function兲 with simulta-
neous icav changes may assist in the determination of the suscepti-
bility of metals to cavitation erosion–corrosion.
The value of icav can be a measure of cavitation erosion–
corrosion failure; however, it does not provide any information
about the degradation rate and the area of the eroded surface. The
following information can be obtained only by impedance data
analysis. Utilization of the electrochemical impedance spectroscopy
共EIS兲 technique is possible only when the conditions of system lin-
earity, causality, and stability are fulfilled. Obtaining a stationary
system during cavitation exposure seems to be impossible because
of the rapidity of the implosion of cavitation bubbles and subsequent
liquid jet impingement. However, application of the EIS technique
was part of the research on cavitation erosion–corrosion
degradation.11,13 The single measurement took about 25 min, while a
significant surface erosion takes place even before that time. The
inductive character of the impedance spectra obtained in the low-
frequency range may be an effect of a nonstable system.
Figure 4. Instantaneous impedance spectra in quiescence period and under cavitation exposure. Each figure refers to single on/off cycle after 共a兲 20, 共b兲 40, 共c兲
60, and 共d兲 80 min.
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DEIS, which is a modification of EIS, was successfully utilized
for the determination of instantaneous impedance spectra of nonsta-
tionary systems such as passive layer cracking,14 Portevin–Le Chat-
elier effect analysis for aluminum alloys,15 pitting corrosion on 304
stainless steel,16 and impedance characteristic determination of re-
dox reactions.17 DEIS gives the possibility of in situ observation of
impedance data variation during cavitation erosion–corrosion expo-
sure of the investigated samples.
Instantaneous impedance spectra in the form of a Nyquist plot
are illustrated for a single cavitation exposure/quiescence cycle in
Fig. 4. The impedance spectra diametrically change as a conse-
quence of cavitation exposure. In quiescence conditions the imped-
ance spectra manifest shape as in the case of diffusion control. In the
period of cavitation exposure the mass transport rate is increased
and the impedance spectra manifest shape as in the case of activa-
tion control. An arc shape is additionally an effect of a rapid corro-
sion product layer failure. The presence of a thin, insoluble surface
film of corrosion products is associated with a small loop at a very
high frequency range during the quiescence period.18 Impedance
spectra under cavitation exposure are also more scattered due to the
chaotic character of the cavitation excitation process.
Diminishing of the impedance loops displayed in the Nyquist
plot is visible as an effect of the cavitation failure in time. This
effect is apparent regardless of the cavitation exposure/quiescence
period 共Fig. 4a-d兲 and is connected with the increase of the surface
roughness and formation of cavities. The drop of the impedance
values as an effect of cavitation exposure was confirmed by Liang
et al.13 The irreversible effect of cavitation exposure on the corro-
sion resistance drop is evident as the impedance loops decrease as a
function of cavitation exposure time, even in the quiescence period.
 Journal of The Electrochemical Society, 155 共4兲 P44-P49 共2008兲
Figure 5. Equivalent circuit describing system under cavitation exposure.
An equivalent circuit for impedance parameter estimation during
cavitation erosion–corrosion exposure is proposed above 共Fig. 5兲.
For the proposed equivalent circuit, Rs represents solution resis-
tance, while Rct and CPEs are the charge transfer resistance and
constant phase element, respectively. CPE is defined with Eq. 4 and
was introduced for double-layer capacitance determination of the
eroded surface
ZCPE = 关Q共j␻兲 兴 n −1
关4兴
In the case of a perfectly smooth surface, n tends to 1. For n = 1
CPE responds to a capacitor of impedance 1/关Q共 j␻兲兴. Changes of
the electric double-layer capacity represented by the Q parameter
are proportional to the changes of surface area of the working elec-
trode, and therefore proportional to the surface roughness. Figures
6-8 illustrate the change of impedance parameters obtained from
modeling of the impedance spectra with the equivalent circuit. Mea-
surements were carried out at different cavitation excitation ampli-
tudes, A0, in order to estimate the influence of the excitation energy
Figure 6. CPE parameters 共a兲 Q and 共b兲 n as a function of cavitation expo-
sure in time, tcav. Operation amplitudes of the piezoelectric transducer equal
to 共䊊兲 12 ␮m, 共△兲 30 ␮m, and 共〫兲 42 ␮m.
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P47
Figure 7. Charge transfer resistance Rct as a function of cavitation exposure
in time, tcav. Operation amplitudes of the piezoelectric transducer equal to
共䊊兲 12 ␮m, 共△兲 30 ␮m, and 共〫兲 42 ␮m.
on material failure rate. During the cavitation exposure, the Q pa-
rameter increased after some period of time. This increase is con-
nected with the development of the surface area. Growth of the Q
element, presented in Fig. 6a, is more rapid for higher cavitation
excitation energies. For a second stage of cavitation exposure, the
material yield point is reached and a high mass of sample can be
observed. The behavior of the n parameter, connected with the sur-
face roughness under cavitation erosion–corrosion exposure, is pre-
sented in Fig. 6b. The most rapid drop of the n parameter is visible
for higher cavitation excitation energies when the surface roughness
is the highest. The increase of n in an early stage of measurement is
hard to explain unequivocally. It may be connected to surface pol-
ishing under the influence of imploding cavitation bubbles, though
this effect requires more research. The Q and n parameters’ change
as a function of cavitation exposure yields the possibility to perform
monitoring of the surface roughness variations.
Primary information about the corrosion resistance during the
cavitation exposure is held by the charge transfer resistance, Rct. It is
apparent in Fig. 7 that during the cavitation exposure its value de-
creases. The corrosion resistance of the material diminishes as an
effect of the erosion load, giving another proof of a high synergistic
interaction between erosion and corrosion in cavitation failure of the
investigated steel. The charge transfer resistance decrease rate is
smaller after a long time of cavitation exposure, where one can see
a smaller difference between surface deformations. This can be ex-
Figure 8. Influence of amplitude of piezoelectric transducer A0 on charge
transfer resistance Rct. tcav = 60 min.
P48 Journal of The Electrochemical Society, 155 共4兲 P44-P49 共2008兲
Figure 9. SEM micrographs of the sample after 60 min of cavitation expo-
sure for different operation amplitudes of piezoelectric transducer: 共a兲 12 and
共b兲 42 ␮m. Magnification 320⫻.
plained by the cushioning effect, which decreases the cavitation ero-
sion rate after a particular depth of degradation is reached.
It is evident that the growth of the corrosion susceptibility, which
can be seen by the inflection point of the Rct function of the cavita-
tion exposure, precedes the mechanical degradation effect of the
sample. This material surface failure effect of the erosion–corrosion
interaction is represented by the Q and n parameter changes.
In Fig. 8 one can see changes of the charge transfer resistance as
a function of the energy of cavitation excitation, given as a square of
the amplitude applied by a piezoelectric transducer, Rct = Rct共A20兲.
This function was extrapolated to A20 = 0, where the Rct value re-
sponds only to the corrosion factor during cavitation exposure. A
comparison of the Rct value for different cavitation excitation am-
plitudes to Rct 共A20 = 0兲 allows an evaluation of the contribution of
the cavitation erosion factor on the corrosion resistance, and hence
determination of the synergistic effect. An increase of the excitation
energy boosts the cavitation erosion–corrosion degradation, fol-
lowed by a drop of Rct values. This is a consequence of the syner-
gistic growth of the corrosion susceptibility simultaneously with the
growth of the cavitation erosion factor. Again, smaller changes of
Rct between higher excitation amplitudes may be explained by a
cushioning effect.
Micrographic pictures of samples subjected to cavitation
erosion–corrosion degradation under different cavitation excitation
amplitudes are presented in Fig. 9. Pictures were made with the use
of a Philips XL30 scanning electron microscope. The exposure time
of cavitation erosion–corrosion tcav equals 60 min. For a 12 ␮m
operation amplitude of the piezoelectric transducer, no cavitation
degradation of the material was observed. The energy delivered to
the sample surface contributed to its polishing, which was compet-
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ing with the corrosion of the investigated sample 共Fig. 9a兲. These
observations are confirmed by only a slight change of the Q and n
parameters 共Fig. 6a and b兲. Scratches apparent on the picture are the
effects of mechanical sample preparation on abrasive paper. On the
other side, for a cavitation excitation amplitude of 42 ␮m, a large
degradation of the surface is visible 共Fig. 9b兲. The whole surface is
covered with cavities; some of them have a diameter as high as
100 ␮m. For high operation amplitudes of the piezoelectric trans-
ducer, the material is imposed to cavitation erosion degradation that
is synergistic with corrosion. The cavitation degradation of the sur-
face, and therefore the high surface roughness, is confirmed by the
considerable change of the Q and n parameters.
Conclusion
Joint erosion–corrosion degradation during cavitation exposure
of samples is an essential degradation agent. In the case of mild
steels, this type of failure, together with corrosion degradation, was
responsible for over 70% of the total mass loss of the sample. Deg-
radation of the investigated samples under the influence of corrosive
environment is significant. Determination of the current technique
for evaluation of cavitation endangerment and erosion–corrosion
degradation rate is necessary.
The authors have presented the results of cavitation erosion–
corrosion degradation of mild steel used as a constructive material.
A slight shift of current icav flowing through the system was corre-
lated with a mass loss function MDPR shift. A large variation of
those parameters was observed in the early stage of the exposure,
followed by stabilization with exposure time. Microscopic images
confirmed that, during the first stage of cavitation exposure, cavities
were formed. Those cavities enlarged afterward, causing a uniform
sample surface failure.
Results acquired by the DEIS technique allow an innovative ap-
proach to cavitation erosion–corrosion degradation evaluation and
monitoring. The influence of cavitation exposure on the impedance
parameters of the investigated samples, as well as on the sample
surface failure rate, is evident. A single cycle of cavitation
exposition/quiescence has shown reversible changes of impedance
due to the failure of the corrosion product layer and an increase of
the mass transport rate. The irreversible character of failure during
the whole period of the experiment was demonstrated in Fig. 6 and
7 and confirmed with scanning electron microscopy 共SEM兲 micro-
graphs in Fig. 9. Additionally, an approach to the evaluation of
cavitation erosion on corrosion resistance synergism was performed
and discussed. Application of the DEIS technique in research on a
cavitation sensor for continuous erosion–corrosion monitoring is
possible and requires further studies.
Acknowledgments
This work has been supported by a grant financed by the Polish
Ministry of Education and Science, N N507 4476 33.
Gdansk University of Technology assisted in meeting the publication
costs of this article.
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