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Corrosion Science 52 (2010) 187–197

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Pitting and uniform corrosion source recognition using acoustic


emission parameters
C. Jirarungsatian, A. Prateepasen *
Department of Production Engineering, Faculty of Engineering, King Mongkut’s University of Technology Thonburi, Bangmod, Toong-kru, Bangkok 10140, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: Acoustic emission (AE) can be used to detect corrosion in various applications. In cases of severe back-
Received 15 December 2008 ground noise, good noise elimination techniques and source identification approaches are required to
Accepted 2 September 2009 increase signal-to-noise ratio. In this paper, a new AE parameter is presented as an alternative to AE activ-
Available online 10 September 2009
ity for classification of corrosion sources. The duration and frequency of AE signals are found to be helpful
in identifying the source of pitting and uniform corrosion processes. Results are explained in terms of the-
Keywords: ories of corrosion mechanisms and AE, as well as using experiment results. Finally, new AE source-based
A. Acid solutions
approaches to monitor both corrosion processes are proposed.
A. Mild steel
A. Stainless steel
Ó 2009 Elsevier Ltd. All rights reserved.
B. Potentiostatic
C. Passive films
C. Pitting corrosion

1. Introduction and literature review problem is that AE activity depends on AE system settings such
as gain and on the severity of the corrosion rate. One possible ap-
Acoustic emission monitoring refers to the detection of tran- proach is the use of AE parameters that vary significantly less with
sient waves during the rapid release of energy from localised corrosive severity, such as duration (assigned as the time interval
sources within a material [1,2]. This in-service test technique ex- between the triggered time of one AE signal (waveform) and the
plores damage due to corrosion [3–7]. Compared to alternative time of disappearance), rise time (assigned as the time interval be-
methods of corrosion monitoring (corrosion coupons analysis, tween the triggering time of AE signal and the time of the peak
electric resistance monitoring, chemical analysis, etc.) [8–10], amplitude), energy (definitions vary across AE system suppliers),
acoustic emission provides a direct measure of failure mechanisms and frequency of AE signal.
in the context of corrosive action. In this paper, a novel technique using AE parameter analyses
Other researchers have shown that acoustic emission signals was implemented to characterise each AE source in a corrosion
are related to corrosion factors (weight loss, density of current) process. The theories of mechanisms and electrochemical charac-
and electrochemical mechanisms [11–19]. However, the acoustic teristics of uniform and pitting corrosion were studied. The condi-
emission as a result of corrosion is usually merged with emissions tions of acoustic bubbles and corrosion mechanisms were
from other nearby acoustic sources. Consequently, it is difficult to considered. Finally, an AE parameter was selected and used to ex-
generate meaningful data in a field environment. Erroneous de- plain and classify sources of AE in both pitting and uniform
tected signals (ones unrelated to corrosion-relevant emissions) corrosion.
may lead to incorrect AE corrosion analysis results. Noisy signals
in the environment can be filtered by signal-conditioning systems. 2. Theoretical background
However, it is difficult to separate the AE noise from the signal.
Various researchers have attempted to identify and characterise 2.1. Mechanisms and electrochemical nature of corrosion processes
AE sources in corrosion processes. Metal damage, passive film rup- [31]
tures and gas bubble activation [20–22] have been proposed as
probable AE sources in corrosion processes. AE activity (hits, events The type of corrosion mechanism and its rate depend on various
and amplitude), acoustic waveforms, and correlation plot analyses factors (material type, corrosive condition, etc.). The corrosion of
[23–30] have partially explained the different AE sources. The steel in an acid environment proceeds according to the overall
reaction: M + 2H+ ? M2+ + H2. This reaction involves ion transfer
* Corresponding author. Tel.: +66 814560121; fax: +66 24709296. between the anode and cathode. Electrochemical reactions in steel
E-mail address: iasaasen@kmutt.ac.th (A. Prateepasen). consist of oxidation and reduction. The oxidation occurs at the

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.09.001
188 C. Jirarungsatian, A. Prateepasen / Corrosion Science 52 (2010) 187–197

anode: M ? M2+ + 2e; the reduction, at the cathode: 2H+ + 2.2.2. Resonant frequencies of bubble break-up
2e ? H2. Bubbles of hydrogen are formed as a corrosion product. To discover the characteristic frequencies of bubble break-up,
Electrochemical polarisation methods are classified as controlled the resonant frequency of bubble oscillation was considered.
potential (potentiostatic, potentiodynamic) and controlled current Acoustic vibrations are typically small in amplitude, which leads
(galvanostatic) approaches. In this work, potentiostatic and poten- to linearisation of the standard wave equation and other simplifi-
tiodynamic methods were used for corrosion control and measure- cations. The radial vibration of a gas bubble in a fluid is modelled
ment. For a potentiostatic method, a potentiostat automatically well as a simple harmonic oscillator, the stiffness and mass param-
adjusts the applied polarising potential between a working electrode eters of which relate to the properties of the gas and fluid. In par-
(WE) and a reference electrode (RE) at any prescribed value to mea- ticular, the inertial mass of the bubble will directly relate to the
sure the current density on a counting electrode (CE). The polarisa- work required to move the surrounding fluid. The bubble will have
tion curve associated with a potentiodynamic method allows a resonant frequency at which it will vibrate after being subjected
detailed study of the important parameters that impact the forma- to an impulsive force. The static pressure in the fluid [P0 ; kg/m2],
tion and growth of passive films (Ecorr) and pit propagation (Epit). the specific heats for the gas [c; J/(kgK)], a Newtonian fluid of con-
stant density [q0 ; kg/m3], and a spherical body of rest radius [R0 ;
2.1.1. Pitting corrosion m] are commonly used to characterise the linear resonant fre-
The initial propagation of pitting corrosion on stainless steel in quency (m0 ) in Hertz [33,34]:
the presence of chloride solution is described in terms of both elec- sffiffiffiffiffiffiffiffiffiffiffi
trochemical and corrosion steps. For simplicity, the elementary pit- 1 3cP0
m0  ð1Þ
ting process can be divided into three phases. First, pit nucleation 2pR0 q0
leads to the formation of a small area of bare, un-filmed passive
surface of metal. Second, the development of a metastable pit leads To determine the acoustic frequency of bubble break-up, we as-
to local dissolution of a significant part of the underlying metal. sume that the resonant frequency of an unstable bubble corre-
The dissolved metal region is referred to as a pit embryo. The result sponds to the break-up frequency. Given Eq. (1), consider the
is either the formation of a stable pit or re-passivation. Subse- maximum diameter of a stable bubble, Dmax, to be the actual size
quently, in the third step, the growth of a stable pit leads to metal of a bubble. The break-up frequency becomes:
damage and pit propagation. sffiffiffiffiffiffiffiffiffiffiffi
The current density can separate the electrochemical analysis of 1 3cP0
mb  ð2Þ
pitting corrosion tests into three stages, pit nucleation, metastable pDmax q0
pit and stable pit, which are described and relate with the acoustic
This estimated frequency is important to identifying acoustic fea-
source in the result analysis section (see Section 4.2).
tures of bubble activity in corrosion processes.
2.1.2. Uniform corrosion
General or uniform corrosion is the name given to the corrosion 2.3. AE sources in corrosion processes
process dominated by uniform thinning, which proceeds without
appreciable localised attack. AE sources in corrosion processes can help evaluate metal dam-
Two theoretical basic stages of the uniform corrosion mecha- age. It is necessary to properly apply signal conditioning. Passive
nism are: film rupture, bubble formation, metal damage and other corro-
sion-relevant phenomena are considered to be sources of AE sig-
(a) The initial stage, in which the primary surface of the metal is nals [35]. Most AE sources reveal information about the
attacked by chemical solutions. The anodic and cathodic mechanism of corrosion and environmental action. Pitting and uni-
sites are virtually inseparable. form corrosion are similar in the case of the gas bubbles generating
(b) A corrosion nucleus propagates on the surface area of the AE signals due to their movement and oscillation [33,34,36].
metal as a uniform corrosive engine. After this phenomenon Acoustic bubble signals can instantaneously drown the emitted
has occurred, the re-passivation of the protective film cannot metal damage signals. These were filtered out by signal condition-
take place. ing hardware. In addition, the AE source from passive film rupture
was only identified at the start of corrosion, except in the case of
In concentrated acidic solutions, the corrosion mechanism pro- corrosion on film-based materials such as stainless steel and cer-
duces substantial amounts of gas. Acoustic emissions can be de- tain alloys. The AE source for pitting corrosion on stainless steel
tected from the bubbles. was from the passive film [25,37]. Pit-based initiation of corrosion
on stainless steel then emitted an AE signal. However, it was diffi-
2.2. Bubbles in the corrosion process cult to identify the AE signal source. Many researchers are working
to solve this problem with additional experiments [25–27].
2.2.1. AE of bubbles
The AE signal from bubble break-up is often detectable. In gen- 2.4. Development of AE-based applications of corrosion analysis
eral, the energy generated from bubble breakage is significant.
Bubble break-up was investigated theoretically and experimen- The objective of AE application development for corrosion anal-
tally. One of the causes of bubble break-up in corrosion processes ysis is to evaluate and predict damage. The first step was to relate
is bubble instability [32]. The upper limit of bubble size is set by AE signal to corrosive damage mechanisms [38]. An application of
the maximum stable bubble size, Dmax, above which the bubble a group of AE sensors presents the time difference for arrival data
is subjected to break-up and becomes unstable. The bubble could to perform source location analysis [39], which has been continu-
break anywhere, including within the liquid or at the surface of ously developed [40]. The classification of corrosion was explored
liquid where the centrifugal force exceeds the surface tension through violent corrosion evaluation by means of acoustic emis-
force. However, the experiment was performed under the same sion and competent classification techniques [41]. Various signal
conditions to reduce the effect of liquid level. The characteristics conditioning methods were developed to increase efficiency [37].
of the released acoustic signals can help identify AE sources from Our research in this field began in 2002 [35–43]. Variables such
corrosion processes. as the type of corrosion [37,36,43] and effects of the environment
C. Jirarungsatian, A. Prateepasen / Corrosion Science 52 (2010) 187–197 189

have been studied [36]. The location of AE sources due to corrosion bubbles (Figs. 1a and 3a), and the other exhibited detectable bub-
was deciphered [39], and development of a new source location bles (Figs. 1b and 3b). The information regarding AE sources from
system was presented [40]. Classifications of corrosion severity the metal damage and passive film rupture was studied by relating
using AE signals were proposed [41] and refined [42]. Identification it to the corrosion mechanism.
of AE sources in corrosion processes was also demonstrated. How-
ever, the AE signal in the field depended not only on the equipment
and conditions but also on environment noise. The use of new AE 3.1. Acoustic emission data acquisition setup
parameters will help address this.
An AE sensor, type R15 from Physical Acoustic Corp. (PAC), was
mounted on the specimen, which was an additional part of the bot-
3. Experimental setup tom tank in the test (see Figs. 1a, 1b and 3a). The AE signal was
amplified by a preamplifier set at 60 dB and filtered by band pass
To discover which AE parameters encode information about AE between 20 and 1200 kHz. The signal was then sent to an AE data
sources from bubbles, the experiment was performed on both acquisition system (LOCAN320 from PAC) to extract AE parameters
pitting and uniform corrosion tests, as shown in Figs. 1 and 3, in the time domain. Background noise was eliminated by setting
respectively. One experiment featured undetectable acoustic the threshold level at 40 dB. The background noise level was

Fig. 1. Two experimental setups of pitting corrosion analysis by AE. (a) Acoustic bubble undetectable. (b) Acoustic bubble detectable.

Fig. 2. The polarisation curve of the SS304 corrosion test in 3% NaCl solution, with a pH of 2 controlled by HCl.
190 C. Jirarungsatian, A. Prateepasen / Corrosion Science 52 (2010) 187–197

Fig. 3. Two experimental setups of uniform corrosion analysis by AE. (a) Acoustic bubble undetectable. (b) Acoustic bubble detectable.

evaluated by the maximum level of the detected signal at the free waves generated by hydrogen bubbles far away from the AE sen-
corrosion condition. sor. Because of this, the acoustic bubbles could not be detected
in Fig. 1a, but they were detectable in Fig. 1b. Although there are
3.2. Specimen preparation and corrosion analysis setup also bubbles within the pit and on the surface of specimen, by
observation, they comprise a very small amount and could be ne-
3.2.1. Pitting corrosion electrochemical setup glected in this work.
Fig. 3 illustrates the equipment used. The specimen was a sheet The electrochemical potential was controlled to replicate corro-
of austenitic stainless steel (SS304) of size 4  6  0.05 cm3 and sive conditions. The electrochemical potential was kept at a level of
used as the working electrode in the electro-chemical process. 0.3041 V(Ag/AgCl/KCl) using the potentiostat to control the pitting
The specimens were prepared by being polished using successive corrosion. Its level was Epit, which was chosen from a potentiody-
grades of wet emery paper up to Mesh No. 1200. They were sub- namic test at 0.5 mV/s polarisation rate, shown as the test result in
jected to passivation treatment at 60 °C for 30 min in 20% HNO3 Fig. 2.
solution. They were then rinsed with de-ionised water, dried by
hot air and left in desiccators overnight. The test was done at room 3.2.2. Uniform corrosion electrochemical setup
temperature in 3% NaCl solution with a pH of 2 controlled by HCl. In Fig. 3, the test specimens were prepared from mild steel of
The solution level was fixed was fixed at 80% height of the test cell type A36. The exposed surface was mechanically ground. The sur-
to neglect the influence of the wave propagation path. The Epit faces were then cleaned with distilled water, dried in a stream of
potentiostatic test was applied to the specimens using a potentio- warm air, and stored overnight in desiccators. In the bubble-free
stat. In Fig. 1a, an electrolytic bridge was used to distinguish sound experiment, Fig. 3a, the exposed surface area of the A36 sample

Fig. 4. The polarisation curve of the A36 steel of corrosion test in H2SO4 solution, pH 4.5. Ecorr was 0.476 V(Ag/AgCl/KCl).
C. Jirarungsatian, A. Prateepasen / Corrosion Science 52 (2010) 187–197 191

was in a solution, the pH of which was adjusted using H2SO4 to 4.5. ing, as one is a subset of the other. In this work, ‘‘duration time” (AE
This pH value was the free bubble condition [44], confirmed by duration) was chosen to correlate with corrosion phenomena be-
monitoring in the experiments. A potentiostat was used to control cause it exhibited high correlation with the corrosion process;
the electrochemical corrosion process at the static corrosive poten- moreover, the duration time at 65 ls can be used to divide the rup-
tial (Ecorr = 0.476 V(Ag/AgCl/KCl). Ecorr was determined from the ture of passive film and pit growth signal (see results in Section
polarisation curve shown in Fig. 4. For the other experiment as a 4.2). It should be remarked that duration time is a time interval be-
non-potential control, with bubbles on the specimen (Fig. 3b), tween the triggered time of one AE signal (waveform) and the as-
the specimen was a sheet of carbon steel (A36) of size signed time of disappearance. In addition, the other parameter,
2.5  20  0.3 cm3, which was set as an angle of 45 degrees with ‘‘frequency,” used in this work was based on the bubble theorem
the tank floor. The concentration of H2SO4 solution was adjusted (see Section 2.2.2).
to a pH of 0.80 by referencing the sulphur concentrate in crude
oil (0.05–2%), which influences corrosion processes in crude oil
4. Results and discussion
storage tanks [44].
In the AE analysis process, AE parameters had been chosen by
In our study, AE sources of pitting and uniform corrosion were
observation of the test results. Previous works showed that many
identified by AE parameters. The bubble activity source was first
AE parameters were related to the corrosion mechanism [35–42].
considered for both corrosion types. The assumption of break-up
However, some AE parameters exhibit identical relations. The scat-
frequency was matched to the recorded characteristics. AE sources
ter plot matrix is a helpful technique to consider the relation of
of passive film rupture and corrosion were identified using corro-
each AE parameter shown in Fig. 5.
sion theorems and electrochemical analysis. The SEM analysis of
A scatter plot matrix is an array of pair-wise scatter plots show-
the specimens after tests is shown in Fig. 6a and b for pitting and
ing the relationship between any pair of AE parameters and the
uniform corrosion, respectively.
corrosion severity. The description ‘‘Rise time” shown at the top
left corner of the scatter plot matrix in Fig. 5 refers to the AE
parameter of rise time. This AE parameter is the value of the y-axis 4.1. Hydrogen bubbles
for all plots along the top row and is the value of the x-axis for all
plots down the first column. Similarly, ‘‘count” refers to the AE First, the identification of bubble phenomena was considered.
parameter of count and applies to the second row and column of The hydrogen bubble size was related to the acoustic resonant fre-
scatter plots in the matrix. The plots that show a linear trend sug- quency, as discussed in Section 2.2. The diameter of each bubble
gest that the two parameters involved are linearly proportional to was measured using image processing techniques, which created
each other. For the experimental data in this work, in Fig. 5, the a scale by referring to the magnified value of the photo. The largest
coherence values in the AE parameters of ‘‘count”, ‘‘energy”, diameter, consistent with our previous work [35], was about 0.9
‘‘amplitude”, and ‘‘duration” are linearly related, which not surpris- mm (stable bubble size, Dmax) for both corrosion tests (see

Fig. 5. The scatter plot of AE parameters and corrosion severity.


192 C. Jirarungsatian, A. Prateepasen / Corrosion Science 52 (2010) 187–197

Fig. 6. Scanning electron microscope analysis (at 100) of specimens after tests. (a) Pitting corrosion. (b) Uniform corrosion.

Fig. 7). Therefore, the break-up frequency of the maximum diame-


ter of the bubble was about 125 kHz, computed using Eq. (2),
where the liquid density and viscosity were 1000 kg/m3 and
0.001 Pa s, respectively. The bubbles were assumed to be filled
with an ideal gas, with c = 1.4 J/(kg K), and the liquid was assumed
to be nearly incompressible, with P0 = 3.110  107 kg/m2.
For the aforementioned reason, the frequency of bubbling used
in this research was above 125 kHz. Further justification for fre-
quencies of bubbling above 125 kHz will be discussed in the next
section in the context of experiments with both undetectable and
detectable bubbles.

4.2. Pitting corrosion analysis

Fig. 7. Gas bubbles on the test specimen in a corrosion process, pH 0.8. Plots of average frequency (kHz) against duration of AE signal
are shown in Fig. 8. Plots of time against duration are in Fig. 9. Figs.

Fig. 8. Source identification on pitting corrosion by AE parameter. (a) All AE sources. (b) Bubble (). (c) Passive film rupture ( ). (d) Pitting corrosion ().
C. Jirarungsatian, A. Prateepasen / Corrosion Science 52 (2010) 187–197 193

Fig. 9. Mechanism and source identification on pitting corrosion by AE. (a) All AE sources. (b) Bubble (). (c) Passive film rupture ( ). (d) Pitting corrosion ().

Fig. 10. AE signal of pitting corrosion tests of an undetectable acoustic bubble.


Fig. 11. The current density of electrochemical analysis of pitting corrosion tests in
three stages: pit nucleation, metastable pit and stable pit.
8a and 9a demonstrate all AE sources, while Figs. 8b, c, d, and 9b, c,
and d refer to each AE source. AE sources for pitting corrosion were
divided into three groups. The resonance frequency of the AE signal ture. Duration can be classified into rupture of passive films and
of above 125 kHz was used to group AEs relevant to bubble rup- pit growth signal sources. These were recorded in terms of AE
194 C. Jirarungsatian, A. Prateepasen / Corrosion Science 52 (2010) 187–197

Fig. 12. The cumulative AE hits of corrosion and film rupture signal, with filtered bubble signal.

Fig. 13. AE source identification of uniform corrosion by frequency. (a) All AE sources. (b) Propagation of corrosion. (c) Bubble breakage.
C. Jirarungsatian, A. Prateepasen / Corrosion Science 52 (2010) 187–197 195

duration at above 65 ls, and below, otherwise. Our assumption stage, the re-passivating film covers the exposed surface areas. This
was based on the dissipated energy as the film rapidly ruptures, causes a reduction in rupture rates of passive films. At this stage,
considering that surface tension forces are higher than atom dislo- the current density change rate of pitting corrosion decreased, as
cation forces in the context of corrosion. The description and evi- shown in Fig. 11. The acoustic signals of bubble source were fil-
dence for separating the AE sources into three different groups is tered by bubbling frequency in Figs. 11 and 12 for easy analysis
further discussed in subsequent sections. of the signals of passive film rupture and pit growth.

4.2.1. Acoustic gas bubbles


As mentioned above, AE signals with frequencies of over 4.2.3. Pit growth or pit propagation
125 kHz were consistent with breakages of bubbles. Figs. 8b and To allow better comparison between the evolutions of the
9b present AE bubble sources. In Fig. 9b, the bubble was created cumulated acoustic activity and the current density during steps
and broken down over the course of the experiment, consistent of corrosion damage (pitting and uniform), the dotted line shown
with our observations. Fig. 10 shows AE signals of pit propagation in Fig. 12 represents the current density apparent in Fig. 11. The
and film rupture obtained from undetectable AE bubbles (Fig. 1a). AEs of pit growth, with the average duration of AE signals of below
Nearly all the AE data were below 125 kHz. 65 ls and with frequency between 3 and 125 kHz, are shown in
Figs. 8d and 9d. In Figs. 9d and 12, pit growth started 1000 s after
4.2.2. Passive film rupture film rupture was confirmed. The cumulative total of detected sig-
AEs of passive film rupture sources, with the duration of AE sig- nals (cumulative hits) of AE from pit growth was lower than that
nals of above 65 ls and with frequencies between 3 and 125 kHz, from film rupture during the pit nucleation stage. The signal was
are shown in Figs. 8c and 9c. In Fig. 9c, AE data with a duration of higher at the next stage of corrosion, as shown in Fig. 12. At the sta-
above 65 ls decrease at the time of initial metastable pit forma- ble pit growth stage, current density became constant, and the
tion, which occurs between 10,000 and 20,000 s. In the metastable number of hits from both AE sources decreased.

Fig. 14. AE source identification of uniform corrosion by average duration time. (a) All AE sources. (b) Propagation of corrosion. (c) Bubble breakage.
196 C. Jirarungsatian, A. Prateepasen / Corrosion Science 52 (2010) 187–197

Fig. 15. Correlation plot of AE parameters of a uniform corrosion test with no acoustic bubble signal.

4.3. Uniform Corrosion Analysis 5.2 AE sources in the context of pitting corrosion can be classi-
fied into three groups using the selected AE parameters,
From the literature, it is clear that AE sources in uniform corro- together with the theory of corrosion mechanisms: (i) gas
sion processes can be categorised into three groups. The first is the bubbles by using their resonant frequency, (ii) passive film
source of damage of the primary metal surface when the corrosion rupture by using duration time and relating to the initial
starts. Next is the nucleation and propagation of corrosion on the time of metastable pit formation according to electrochem-
metal, called uniform corrosion. The last involves the gas bubble ical analysis, and (iii) pit propagation as related to the time
breaking up during the corrosion process. of occurrence and pitting corrosion mechanisms.
A resonant frequency of above 125 kHz in the context of gas 5.3 AE sources in uniform corrosion scenarios can be divided
bubble break-up is equal to that in the pitting corrosion case. It into two categories, namely, gas bubble and uniform corro-
can be used to separate AE sources into two groups, as shown in sion. The categorisation can be determined using the key
the correlation plot, between average filter and duration, as shown AE parameters of resonant frequency.
in Fig. 13. In Fig. 14, the AE sources were divided into two groups 5.4 A novel technique that uses the selected AE parameters
according to AE average durations. instead of AE activity was presented. The benefit of this
approach is that one can better classify AE sources. Signals
4.3.1. Acoustic gas bubble from actual AE sources can be derived and processed. In
We considered a bubble resonant frequency above 125 kHz, addition, the resulting information is essential to separate
which is the same frequency as that in the pitting corrosion test noise from signal in corrosion applications.
case. The bubble size in both pitting and uniform corrosion tests
was similar, as measured by image analysis. In addition, the aver- Acknowledgements
age duration was about 350 ls.
The authors thank The Thailand Research Fund for supporting
4.3.2. Metal damage in the uniform corrosion scenario this research.
Through uniform corrosion signal analysis, it became clear that
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